Oral Care Compositions Comprising Fluoride Ions

ABSTRACT

Oral care compositions and/or unit-dose oral care compositions with a fluoride ion source. Oral care compositions and/or unit-dose oral care compositions with a high average fluoride ion uptake. Oral care compositions with one or more web forming materials, a calcium ion source, and a fluoride ion source with a high average fluoride uptake.

FIELD OF THE INVENTION

The present invention relates to oral care compositions comprising afluoride ion source. The present invention also relates to unit-doseoral care compositions comprising a fluoride ion source. The presentinvention also relates to oral care compositions and/or unit-dose oralcare compositions with a high average fluoride ion uptake.

BACKGROUND OF THE INVENTION

Dentifrice compositions are typically formulated as a paste that can besqueezed out of a tube. Dentifrice compositions can include metal ions,fluoride ions, abrasives, calcium sources, surfactants, whiteningagents, humectants, thickening agents, and other formulationingredients. Typically, dentifrice compositions must be carefullyformulated to avoid reactivity in the tube, but retain reactivity in theoral cavity. In many cases, ingredients must be substituted or removedto balance reactivity in the tube with in mouth benefits.

Specifically, fluoride ions sources, such as sodium fluoride, stannousfluoride, and/or sodium monofluorophosphate, among others, can be addedto dentifrice compositions to deliver anti-caries benefits. However,fluoride ion sources can be difficult to incorporate into dentifriceand/or oral care compositions due to the reactivity between fluorideions and other dentifrice components, such as calcium ions.

Fluoride ions provide an anticavity benefit through the uptake offluoride ions into enamel. The interaction of fluoride with the mineralcomponent of teeth (known as hydroxyapatite or HAP) produces afluorohydroxyapatite (FAP) mineral, through the substitution of OH⁻ inHAP with F⁻. Fluoride incorporation into the dental enamel as FAPresults in increased hydrogen bonding, a denser crystal lattice, and anoverall decrease in the solubility of dental enamel. The incorporationof fluoride into the hydroxyapatite (HAP) lattice may occur while thetooth is forming or by ion exchange after it has erupted. Additionally,enamel solubility decreases with increasing amounts of fluorideincorporation. Thus, fluoride is routinely added to dentifrice and mouthrinses to strength the dental enamel of teeth.

Unfortunately, fluoride bioavailability can be significantly altered dueto (i) chemical reactivity between the fluoride ion and othercomponents, such as calcium ions, abrasive systems, chelants, andwhitening agents, (ii) hydrolysis, and (iii) oxidation. Thus, fluoridebioavailability of fluoride ions in a paste are impacted based on theconcentration and presence of other reactive components as a function oftime as many fluoride compounds are prone to hydrolyze and/or oxidizewhile in the aqueous phase.

Thus, the incorporation of fluoride ions into dentifrice compositions isonly possible by minimizing interactions between fluoride ions and otherdentifrice components during storage to maximize fluoride ionavailability for reactivity with oral cavity surfaces, such as enamel,dentine, gums, plaque, and bacteria. Accordingly, there is a need for anoral care composition that minimizes reactivity between fluoride ionsources and other dentifrice components.

SUMMARY OF THE INVENTION

Disclosed herein is a unit-dose oral care composition comprising (a) afibrous composition formed from one or more web forming materials; (b) afluoride ion source; and (c) an abrasive.

Disclosed herein is an oral care composition comprising (a) one or moreweb forming materials; (b) a calcium ion source; and (c) a fluoride ionsource, wherein the oral care composition has an average fluoride uptakeof at least about 1000 ppm.

Disclosed herein is an oral care composition comprising (a) one or morenonwoven web layers comprising (i) one or more web forming materials,and (ii) a fluoride ion source; and (b) a nonfibrous composition, thenonfibrous composition comprising a calcium ion source.

Disclosed herein is an oral care composition comprising (a) one or morenonwoven web layers comprising (i) one or more web forming materials,and (ii) a calcium ion source; and (b) a nonfibrous composition, thenonfibrous composition comprising a fluoride ion source.

Disclosed herein is an oral care composition comprising (a) one or morenonwoven web layers, the one or more nonwoven web layers comprising (i)one or more web forming materials, and (ii) a metal ion sourcecomprising a stannous ion source, a zinc ion source, or combinationsthereof; and (b) a nonfibrous composition, the nonfibrous compositioncomprising an abrasive.

Disclosed herein is an oral care composition comprising (a) one or morenonwoven web layers, the one or more nonwoven web layers comprising (i)one or more web forming materials, and (ii) an abrasive (b) a nonfibrouscomposition, the nonfibrous composition comprising a metal ion sourcecomprising a stannous ion source, a zinc ion source, or combinationsthereof.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to oral care compositions comprising afluoride ion source. The present invention also relates to unit-doseoral care compositions comprising a fluoride ion source. The presentinvention also relates to oral care compositions and/or unit-dose oralcare compositions with a high average fluoride ion uptake.

Fluoride ion sources can be difficult to formulate in oral carecompositions due to reactivity with other ingredients in the oral carecompositions and/or the oxidation or hydrolysis of fluoride ion sourcesin aqueous oral care compositions.

The present invention is directed to oral care compositions that useassembled design to physically separate fluoride ions from otherreactive components of the oral care composition. For example, thefluoride ion can be in one location of the oral care composition and thecalcium ion source or calcium abrasive can in a separate location of theoral care composition. While dentifrice reactivity is typicallymanipulated through formulation design, the use of nonwoven webs willallow for dentifrice reactivity to be dramatically lowered by separatingcomponents by placing them in the solid phase, where reactivity islower, or physically separating the ingredients through assembly designof the oral care composition.

Definitions

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2nd Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied.

The term “oral care composition” as used herein means a product that inthe ordinary course of usage is retained in the oral cavity for a timesufficient to contact some or all of the dental surfaces and/or oraltissues for purposes of oral health. In one embodiment, the compositionis retained in the oral cavity to deliver an oral care active agent. Theoral composition of the present invention may be in various formsincluding toothpaste, dentifrice, tooth gel, tooth powders, tablets,rinse, sub gingival gel, foam, mousse, chewing gum, lipstick, sponge,floss, prophy paste, petrolatum gel, denture product, nonwoven web, orfoam. In one embodiment, the oral composition is in the form of anonwoven web. In another embodiment, the oral composition is in the formof a dentifrice. The oral composition may also be incorporated ontostrips or films for direct application or attachment to oral surfaces orincorporated into floss. The oral care composition may also be a stripthat can be directly applied to a surface of the oral cavity. The stripcan at least partially dissolve upon contact with moisture or brushing.

The term “orally acceptable carrier” as used herein means a suitablevehicle or ingredient, which can be used to form and/or apply thepresent compositions to the oral cavity in a safe and effective manner.

The term “effective amount” as used herein means an amount of a compoundor composition sufficient to induce a positive benefit, an oral healthbenefit, and/or an amount low enough to avoid serious side effects,i.e., to provide a reasonable benefit to risk ratio, within the soundjudgment of a skilled artisan. Depending on the type of oral healthbenefit and the efficacy of active compound, “effective amount” means atleast about 0.0001% of the material, 0.001% of the material, or 0.01 ofthe material, by weight of the composition.

The term “dentifrice” as used herein means paste, gel, powder, tablets,or liquid formulations, unless otherwise specified, that are used toclean, treat, or contact the surfaces of the oral cavity. Additionally,as disclosed herein, the dentifrice means a nonwoven web that are usedto clean the surfaces of the oral cavity. The term “teeth” as usedherein refers to natural teeth as well as artificial teeth or dentalprosthesis.

As used herein, the term “filament” means a thin, flexible threadlikeobject that can be used to form a nonwoven web of the present type. Thelength of a filament can greatly exceed its diameter, i.e. a length todiameter ratio of at least about 5, 10, or 25.

The filaments of the present invention may be spun from nonwoven webforming materials via suitable spinning operations, such as meltblowingor spunbonding.

Filaments are typically considered continuous or substantiallycontinuous in nature. Filaments are relatively longer than fibers.Non-limiting examples of filaments can include meltblown filaments,spunbond filaments, and combinations thereof. In one embodiment, thefilaments are meltblown filaments.

In one example, the filaments may be in the form of fibers, such as whenthe filaments are cut to shorter lengths. Thus, in one example, thepresent invention also includes a fiber comprising the composition ofthe filament of the present invention.

As used herein, “nonwoven web forming material” means a composition thatis suitable for making a filament such as by meltblowing, spunbonding,or fluid film fibrillation. The nonwoven web forming material comprisesone or more nonwoven web forming materials that exhibit properties thatmake them suitable for spinning into a filament.

As used herein, “length”, with respect to a filament, means the lengthalong the longest axis of the filament from one terminus to the otherterminus. If a filament has a kink, curl or curves in it, then thelength is the length along the entire path of the filament.

As used herein, “average diameter”, with respect to a filament, ismeasured according to the Diameter Test Method described herein.

As used herein, the term “disintegratable” and “disintegration” meansthat the oral care composition, filament, or nonwoven is reduced tocomponents, fragments or compositions when exposed to conditions ofintended use.

As used herein, the term “dissolves” means that the oral carecomposition, filament, or nonwoven web is mostly or completelysolubilized. The oral care composition may appear to visibly dissolveeven though some of the components do not completely dissolve—forexample cross linked polyacrylic acid polymers form clear gels givingthe appearance of dissolution while, not wishing to be bound by theory,the clear gels are simply hydrated. Another example is an abrasive whichdoes not dissolve at all even though it may make up the majority of thecomposition. An oral composition comprising an abrasive would still bedeemed to be “dissolved” if only the abrasive has not dissolved.Dissolution of the oral care composition is complete when any remainingparticles have a diameter of 2 mm or less.

As used herein, the term “applying” includes spraying, dusting,sprinkling, coating, surface-printing (e.g., in the shape of a desiredadornment, decoration, or pattern), pouring on, injecting into theinterior, dipping, or by any other suitable means, such as by use of adepositor, sifter, or powder bed.

As used herein, “conditions of intended use” means the temperature,physical, chemical, and/or mechanical conditions that an oral carecomposition comprising one or more filaments of the present invention isexposed to when the oral care composition is used for its designedpurpose. The oral care compositions of the present invention can beadministered to a mammal via the oral cavity, mouth, throat, andcombinations thereof. The conditions of intended use can be thetemperature, physical, chemical, and/or mechanical conditions in theoral cavity, mouth, and/or throat of a mammal.

“Triggering condition” as used herein means anything, as an act or eventthat serves as a stimulus and initiates or precipitates a change in thefilament, such as a loss or altering of the filament's physicalstructure and/or a release an oral care active including dissolution,hydration, and swelling. Some triggering conditions include a suitablepH, temperature, shear rate, or water content.

“Morphology changes” as used herein with respect to a filament'smorphology changing means that the filament experiences a change in itsphysical structure. Non-limiting examples of morphology changes for afilament of the present invention include dissolution, melting,swelling, shrinking, breaking into pieces, lengthening, shortening,peeling, splitting, shredding, imploding, twisting, and combinationsthereof. The filaments of the present invention may completely orsubstantially lose their filament physical structure or they may havetheir morphology changed or they may retain or substantially retaintheir filament physical structure as they are exposed to conditions ofintended use.

As used herein, a “web” means a sheet of continuous filaments or fibersof any nature or origin that have been formed into a web by any means,and bonded together by any means.

As used herein and as defined by European Disposables and NonwovensAssociation (EDANA), “nonwoven web” means a sheet of continuousfilaments or fibers of any nature or origin that have been formed into aweb by any means, and bonded together by any means, with the exceptionof weaving or knitting. Felts obtained by wet milling are not nonwovens.In one example, a nonwoven web according to the present invention meansan orderly arrangement of filaments within a structure in order toperform a function. In one example, a nonwoven web of the presentinvention is an arrangement comprising a plurality of two or more and/orthree or more filaments that are inter-entangled or otherwise associatedwith one another to form a nonwoven web.

The term RDA refers to Relative Dentin Abrasion or Radioactive DentinAbrasion as defined in FDI-ISO 11609. The term PCR refers to PellicleCleaning Ratio as defined in the original paper by Stookey et al. 1982and later used by Schemehorn et al. 2011 to characterize the relativeeffectiveness of oral care compositions to remove a laboratory-sourced,human-like, stain from enamel chips. These experimental techniques willbe described in greater detail later.

All percentages and ratios used hereinafter are by weight of totalcomposition, unless otherwise indicated. All percentages, ratios, andlevels of ingredients referred to herein are based on the actual amountof the ingredient, and do not include solvents, fillers, or othermaterials with which the ingredient may be combined as a commerciallyavailable product, unless otherwise indicated. All measurements referredto herein are made at 25° C. unless otherwise specified.

The composition, process and methods of the present invention cancomprise, consist of, or consist essentially of, the essential elementsand limitations of the invention described herein, as well as anyadditional or optional ingredients, components, or limitations describedherein or otherwise useful in oral care compositions intended for use orconsumption by mammals preferably consumption or use by humans.

Unit-Dose Oral Care Composition

The oral care compositions of the present invention can be unit-doseoral care compositions. A unit-dose oral care composition is an amountof the oral care composition to be administered to a patient or consumerin a single use. The unit-dose oral care composition can be a unit-dosedentifrice, a unit-dose mouth rinse, a unit-dose tooth gel, a unit-dosetooth whitening composition, or any other suitable unit-dose oral carecomposition capable of being retained in the oral cavity for a timesufficient to contact some or all of the dental surfaces and/or oraltissues for purposes of oral health.

The amount, in mass and/or volume, of the unit-dose oral carecomposition is determined based on the desired type of unit-dose oralcare composition. For example, a unit-dose dentifrice can be sized todeliver the correct amount of fluoride in a single use according tolocal laws and regulations, such as the U.S. Food and DrugAdministration (FDA) monograph, which allows formulations of 850 to 1150ppm and/or 1500 ppm of fluoride ions. Additionally, a unit-dosedentifrice can be sized to deliver the correct amount or ratio of otheringredients, such as, for example, antimicrobial agents, abrasives,surfactants, flavors, metal ions, etc. Similarly, a unit-dose mouthrinse can be sized to deliver the correct amount of mouth rinseingredients, such as, for example, fluoride ions, antimicrobial agents,abrasives, surfactants, flavors, metal ions, etc.

The unit-dose oral care composition can be in the form of a pouch, adroplet, a solid open cell foam, a solid closed cell foam, a fibrouscomposition, a paste composition, a gel composition, a tabletcomposition, a strip composition, a tape composition, and/or an assemblyof one or more of the forms described in this paragraph.

The unit-dose oral care composition can be sized to fit a manualtoothbrush, an electric toothbrush, or any other applicator designed tohelp contact the unit-dose oral care composition to the surfaces of theoral cavity, including, but not limited to teeth.

The unit-dose oral care composition of the present invention can be asubstantially flat or flat composition in the form of a pad, strip,tape, or tablet having a thickness of from about 0.05 millimeter (mm) toabout 20 mm, from about 0.05 mm to about 10 mm, from about 0.05 mm toabout 5 mm, from about 0.5 mm to about 1 mm, from about 0.05 mm to about0.5 mm, from about 0.05 mm to about 0.25 mm, or from about 0.05 mm toabout 0.1 mm, as measured by the Thickness Method described hereafter.The unit-dose oral care composition can be formed into a cylindricalshape (e.g. by rolling) having a length from about 0.5 centimeter (cm)to about 10 cm, from about 1 cm to about 5 cm, or from about 1.5 cm toabout 3 cm. The unit-dose oral care composition can be a rectangularprism including a cube wherein the longest sides of the rectangularprism has a length from about 5 mm to 20 mm, from about 10 mm to 15 mm,or from about 5 mm to about 10 mm, as measured by the Thickness Methoddescribed herein. If the dimensions of the dose changes, the basisweight of the dose can change. The unit-dose oral care composition canbe circular or an oval wherein the diameter of the circle or the lengthof the longest portion of the oval is from about 5 mm to about 5 cm, 5mm to about 100 mm, 5 mm to about 50 mm, 1 cm to about 5 cm, or 100 mmto about 1 cm.

The unit-dose oral care composition can be in the form of one or moreflat sheets or pads of an adequate size to be able to be handled easilyby the user. The unit-dose oral care composition can comprise oneunit-dose of one or more oral care actives that can provide one or moreoral care benefits and/or treat one or more oral care conditions. Theunit-dose oral care composition may have a square, rectangle, oval,circular, disc shape or any other suitable shape. The unit-dose oralcare composition can also be in the form of a continuous strip includingdelivery on a tape-like roll dispenser with individual portionsdispensed via perforations and/or a cutting mechanism.

A unit-dose oral care composition can allow for the dose to includeincompatible components within the same composition. Components areconsidered incompatible with one another, if when they are in the samesolution or as non-solid mixtures, at least one of the components has asignificant reduction in efficacy, stability, or bioavailability.Incompatible components can be components that chemically interact witheach other to form new compounds, complexes and/or salts and/orcomponents that will separate into discrete portions or phases of thecomposition to minimize unfavorable interactions.

Examples of incompatible components can include, but are not limited to,metal ion sources and silica abrasives, metal ion sources andpolyphosphates, metal ion sources and pyrophosphates, calcium ionsources and fluoride ion sources, calcium ion sources and phosphatesalts, calcium ion sources and pyrophosphate, oxalate ions and peroxidecompounds, stannous fluoride and peroxide compounds, cationicantimicrobial agents, such as cetyl pyridinium chloride, and fluorideion sources, acids and bases, calcium ion sources and chelants, such asEDTA, oxidizing agents and reducing agents, hydrophobic components, suchas petrolatum, silicones, polybutene, and hydrophilic components, suchas water and alcohols, and/or any other incompatible components, asdefined above.

The unit-dose oral care compositions, as described herein, can bedesigned to maximize bioavailability, stability, and/or efficacy of theingredients by minimizing reactivity between the ingredients. Minimizingreactivity between the ingredients can be accomplished by physicallyseparating the ingredients into discrete portions of the composition orby placing one or more ingredients in the solid phase where reactivityis lower.

In the context of a pouch composition, the interior volume can beseparated into multiple discrete, layered, adjacent, and/or superimposedportions that can place one or more components in each portion. Forexample, a fluoride ion source can be in one portion while a calcium ionsource can be in another portion of the pouch composition. Additionally,a metal ion source can be in one portion while a silica abrasive orpolyphosphate can be in another portion of the pouch composition.

In the context of a fibrous oral care composition, one or more reactivecomponents can be in a one nonwoven web layer and one or more reactivecomponents can be in another nonwoven web layer. Additionally, one ormore reactive components can be in one or more nonwoven web layers andone or more reactive components can be between, on top, below, foldedwithin, adjacent, or superimposed with the one or more nonwoven weblayers, such as in a nonfibrous composition. For example, a fluoride ionsource can be spun within or comingled with a first fibrous compositioncomprising one or more nonwoven web layers and a calcium ion source canbe spun within or comingled with a second fibrous composition comprisingone or more nonwoven web layers. The first and second fibrouscompositions can be assembled into a single multi-ply composition usingany suitable means. Additionally, a fluoride ion source can be spunwithin or comingled with a fibrous composition comprising one or morenonwoven web layers and a calcium ion source can be in a nonfibrouscomposition, as a solid composition or at least partially dissolved orat least partially dispersed in a liquid composition. The fibrouscomposition and the nonfibrous composition can be assembled into amulti-ply composition or the nonfibrous composition can be can bebetween, on top, below, folded within, adjacent, or superimposed withthe fibrous composition.

In the context of a foam oral care composition, such as a flexibleporous dissolvable solid structure, the reactive components can bewithin or comingled together within an open cell or closed cell foam,the foam compositions are described in US 2011/0027328, which is hereinincorporated by reference. One or more reactive components can be in thefoam composition, while one or more reactive components can be in anonfoam composition, such as a surface resident particulate coating,which coats the surface of the solid foam composition.

The use of a unit-dose oral care composition, as described herein,allows for easy portability and the ability to better control dosing.For example, due to current restrictions on airlines regarding liquidproducts, a passenger is limited to carrying on only a small amount ofmouth rinse or dentifrice or to packing his mouth rinse or dentifrice inhis checked luggage. If the oral care composition were in unit-doseform, the passenger can pack exactly the amount needed into a carry-onwithout the need to worry about airline packing restrictions.

Fibrous Oral Care Composition

The oral care composition can be a fibrous oral care composition. Thefibrous oral care composition can comprise a fibrous composition and/ora nonfibrous composition. The fibrous composition can comprise at leastone web. The fibrous composition can comprise a nonwoven web and/or awoven web.

The fibrous composition can comprise one or more web layers. The one orweb layers can comprise one or more filaments and/or fibers. The oralcare composition may comprise a first web and a second web wherein thefirst and the second web comprise different components.

The fibrous composition can comprise any suitable oral care component.The fibrous composition can comprise any component described herein.

The web can comprise more than one filament. The web can comprise afirst filament and a second filament both comprising an oral care activeand the oral care active can be the same oral care active or differentoral care actives. The web can comprise a first filament comprising animmediate delivery oral care active and a second filament comprising anextended delivery, a delayed delivery, and/or a targeted delivery oralcare active. The web can comprise a first filament, a second filament,and a third filament, wherein each filament comprises a different oralcare component.

The web or oral care composition can comprise a plurality of identicalor substantially identical, from a compositional perspective, filamentsaccording to the present invention. The web or oral care composition maycomprise two or more different filaments according to the presentinvention. Non-limiting examples of differences in the filaments may bephysical differences such as differences in diameter, length, texture,shape, rigidness, elasticity, and the like; chemical differences such ascrosslinking level, solubility, melting point, glass transitiontemperature (Tg), web forming material, color, amount of oral careactive, amount of web forming material, presence of a coatingcomposition on the oral care composition, chemical composition of theoral care active including whether the oral care active is immediatedelivery, delayed delivery, extended delivery, or targeted delivery, andthe like; differences in whether the filament loses its physicalstructure when the filament is exposed to conditions of intended use;differences in whether the filament's morphology changes when thefilament is exposed to conditions of intended use; and differences inwhen and where the benefit from the oral care active is experienced. Inone example, two or more filaments within the oral care composition orweb may comprise the same web forming material, but have different oralcare actives.

The web can comprise two or more filaments wherein the filaments releasethe oral care actives at different rates. The different rates may becaused by the filaments being positioned at an external surface of theweb.

The oral care composition can comprise a nonfibrous composition, whichmay or may not be greater in weight percentage, by weight of the oralcare composition, than the fibrous composition. The nonfibrouscomposition can be between a first web and a second web. At least aportion of the nonfibrous composition can be in contact with a surfaceof fibrous composition. The nonfibrous composition can be placed on asingle web layer and the web layer can be folded on top of thenonfibrous composition, rolled with the nonfibrous composition, placedon top of or below the fibrous composition, and/or the fibrouscomposition can wrap around the fibrous composition.

The nonfibrous composition can comprise any suitable oral carecomponent. The nonfibrous composition can comprise any componentdescribed herein. The nonfibrous composition can be liquid, solid,aqueous, and/or combinations thereof.

The oral care composition of the present invention can have a basisweight of from about 10 grams per square meter (g/m²) to about 5000g/m², from about 25 g/m² to about 2500 g/m², from about 40 g/m² to about1500 g/m², or from about 500 g/m² to about 2000 g/m².

The fibrous oral care composition can comprise two or more components ororal care actives that are generally considered incompatible, asdescribed herein. For example, a first web layer can comprise a fluorideion source and a second web layer can comprise a calcium ion source. Inanother example, a first web layer can comprise a metal ion source, suchas a stannous ion source, and a nonfibrous composition can comprise asilica abrasive or a polyphosphate.

The oral care composition or web may exhibit different regions, such asdifferent regions of basis weight, density and/or caliper. The oral carecomposition or web may comprise discrete regions of filaments thatdiffer from other parts of the web.

The oral care composition or the web may comprise one or more textured,dimpled or otherwise topographically patterned surfaces includingletters, logos or figures. The textured oral care composition can resultfrom the shape of the filament or the web, in that the outermost surfaceof the composition contains portions that are raised with respect toother areas of the surface. The raised portions can result from theformed shape of the oral care composition, for example the web can beformed in a dimpled or waffle pattern. The raised portions can also bethe result of creping processes, imprinted coatings, embossing patterns,or the result of the physical form of the composition itself.

The web of the present invention may be pressed into a film to form theoral care composition; this can be done by applying a compressive forceand/or heating the web to convert the web into a film. The film cancomprise the oral care actives that were present in the filaments of thepresent invention. The web may be completely converted into a film orparts of the web may remain in the form of a film after partialconversion of the web into the film. The oral care composition mayconstitute one or more webs wherein at least one of the webs has beenpressed into a film. The oral care composition may comprise two or morewebs that have been pressed into a film.

The web can be rolled, compressed, cut, or stacked to form a threedimensional oral care composition. For instance, the web may becompressed into a pill or tablet, rolled into a cylinder, or compressedor stacked into a rectangular prism to form the oral care composition.

The oral care composition may constitute one or more layers of webswhich are optionally bonded together via a bonding means (includingheat, moisture, ultrasonic, pressure etc.). The oral care compositionmay constitute one or more layers of webs which are optionally bondedtogether via compression.

The oral care composition or nonwoven web can be perforated with holesor channels penetrating into or through the oral care composition, intotal, or locally in one or more web layers.

These perforations can be formed as part of making the web or oral carecomposition via spikes extended from the surface of an adjacent belt,drum, roller or other surface. Alternatively, these perforations can beformed after forming the web or oral care composition by a process ofpoking or sticking the porous solids with pins, needles or other sharpobjects.

Filament

The oral care composition can comprise one or more filaments. In anembodiment, the filaments of the present invention exhibit a length ofgreater than about 0.1 in., in an alternate embodiment greater thanabout 0.2 in, in still another embodiment greater than about 0.3 in, andin another embodiment greater than about 2 in.

The filaments can have an average diameter of less than about 150micrometers (μm), less than about 100 μm, less than about 10 μm, or lessthan about 1 m with a relative standard deviation of less than 100%,less than 80%, less than 60%, or less than 50%, such as in the range of10% to 50%, for example. As set forth herein, the significant numbermeans at least 10% of all the filaments, in another embodiment at least25% of all the filaments, in another embodiment at least 50% of all thefilaments, in yet another embodiment at least 75% of all the filaments.The significant number may be at least 99% of all the filaments. Atleast 50% of all the filaments may have an average diameter less thanabout 10 μm. The filaments produced by the method of the presentdisclosure can have a significant number of filaments with an averagediameter less than about 1 μm, or sub-micron filaments. In anembodiment, the oral care composition can comprise at least 25% of allthe filaments with an average diameter less than about 1 μm, at least35% of all the filaments with an average diameter less than about 1 μm,at least 50% of all the filaments with an average diameter less thanabout 1 μm, or at least 75% of all the filaments with an averagediameter less than about 1 μm.

The filament can comprise less than 30% moisture, by weight of thefilament, less than 20% moisture, by weight of the filament, less thanabout 10% moisture, by weight of the filament, less than about 5%moisture, by weight of the filament, less than about 3%, by weight ofthe filament less than about 1%, or less than about 0.1%, by weight ofthe filament.

The filament of the present invention can be monocomponent ormulticomponent. The filament can be a bicomponent filament. The filamentcan be a tricomponent filament. The multicomponent filament may be inany form, such as side-by-side, core and sheath, islands-in-the-sea andthe like.

The filaments of the present invention may be meltblown filaments. Thefilaments of the present invention may be spunbond filaments. Thefilaments may be hollow filaments prior to and/or after release of oneor more of its active agents.

The filament may comprise an oral care active within the filament and anoral care active on an external surface of the filament, such as acoating on the filament. The oral care active on the external surface ofthe filament may be the same or different from the active agent presentin the filament. If different, the oral care actives may be compatibleor incompatible with one another.

Solid Foam Compositions

The oral care composition can be a solid foam composition, such as theflexible porous dissolve solid structure described in US 2011/0027328,which is herein incorporated by reference. The solid foam compositioncan be in the form of an open cell foam or a closed cell foam.

The solid foam composition can comprise any suitable oral carecomponent. The solid foam composition can comprise any componentdescribed herein. The solid foam composition can comprise a surfaceresident coating composition. The surface resident coating compositioncan comprise any suitable oral care component or any component describedherein.

Importantly, U.S. Patent Application No. 2011/0027328 does not disclose,teach, or suggest that the amount of pyrophosphate must be minimized inorder to produce solid soluble foams. In fact, U.S. Patent ApplicationNo. 2011/0027328 only teaches example foam compositions with a highamount of pyrophosphate. As such, it was unexpectedly found here thatpyrophosphate interfered with the foam composition formation process.

Thus, the solid foam compositions of the present invention comprise afoam forming material, one or more surfactants, a plasticizer, andwherein the solid foam composition has less than about 5%, less thanabout 1%, or free of an inorganic metal salt, a polyphosphate, orspecifically, a pyrophosphate. The foam forming material is any suitablematerial that exhibits properties suitable for making a foam.Non-limiting examples of foam forming materials can include thewater-soluble polymer disclosed by U.S. Patent Application No.2011/0027328.

Web Forming Material

The web can be formed by any suitable means. The web can comprise spunfibers and/or spun filaments. The nonwoven web can be made from a webforming material or nonwoven web forming material as described in U.S.patent application Ser. No. 16/250,455, U.S. patent application Ser. No.16/250,484, U.S. Pat. Nos. 9,139,802, 9,175,250, and/or 8,785,361, whichare herein incorporated by reference in their entirety.

The web forming material can comprise any suitable material thatexhibits properties suitable for making a fiber or filament.Non-limiting examples of web forming materials can include polymers,polyols, sugars, sugar alcohols, and combinations thereof. The web cancomprise two or more different web forming materials. The web cancomprise three or more different web forming materials. The polymer canfunction as a web forming material and in certain embodiments can alsoprovide an oral health benefit.

The fibrous composition can comprise from about 1% to about 100%, fromabout 2% to about 50%, from about 5% to about 35%, from about 5% toabout 20%, from about 1% to about 15%, or from about 5% to about 10% ofa nonwoven web forming material, by weight of the fibrous composition.

The oral care composition can comprise from about 1% to about 80%, fromabout 1% to about 50%, from about 1% to about 25%, from about 2% toabout 20%, from about 3% to about 15%, less than about 10%, or fromabout 5% to about 10% of a web forming material by total weight of theoral care composition.

Polymer

The oral care composition can comprise a polymer. The web formingmaterial can comprise a polymer. The fibrous composition or thenonfibrous composition can comprise a polymer. The foam composition cancomprise a polymer. Non-limiting examples of polymers can includenaturally sourced polymers, synthetic polymers, and combinationsthereof.

Non-limiting examples of naturally sourced polymers can includealginates, gums, protein-based polymers, starch-based polymers, nativestarches, modified starches, fiber polymers, other naturally sourcedpolymers, and combinations thereof.

Non-limiting examples of alginates can include ammonium alginate,calcium alginate, potassium alginate, propylene glycol alginate, andcombinations thereof.

Non-limiting examples of gums can include acacia gum, carrageenan,tragacanth gum, guar gum, locust bean gum, xanthan gum, gellan gum, andcombinations thereof.

Non-limiting examples of protein-based polymers can include whey proteinisolate, soy protein isolate, egg albumin, casein, collagen, glutelin,gelatin, gluten, zein, and combinations thereof.

Non-limiting examples of starch-based polymers can include thosestarch-based polymers sourced from cereals, tubers, roots, legumes,fruits, and combinations thereof. Starch-based polymers can includeglucose monomers joined in an a 1,4 linkage, amylose, amylopectin, andcombinations thereof.

Non-limiting examples of native starches can include can include waxy orhigh amylase varieties of corn, pea, potato, banana, barley, wheat,rice, sago, amaranth, tapioca, arrowroot, canna, sorghum, andcombinations thereof.

Non-limiting examples of modified starches can include hydroxypropylstarch, maltodextrin, high amylose starch, and combinations thereof.

Non-limiting examples of fiber polymers can include pectins,fructo-oligosaccharides, inulin, agar, beta-glucans, dextrins, lignin,celluloses, non-starch polysaccharides, reduced starch, polycarbophil,citrus fiber, and combinations thereof.

Non-limiting examples of other naturally sourced polymers can includeagar, pullulan, chitin, chitosan, shellac, and combinations thereof.

Non-limiting examples of synthetic polymers can include cellulosederivatives, carbomers, polymethacrylates, other synthetic polymers, andcombinations thereof.

Non-limiting examples of cellulose derivatives can includehydroxyethylmethyl cellulose, hydroxylpropylmethyl cellulose,hydroxypropyl cellulose, hydroxypropylethyl cellulose, methylcellulose,hydroxypropyl methylcellulose, and combinations thereof.

Non-limiting examples of carbomers can include carbomer 934, carbomer934P, carbomer 940, carbomer 94, carbomer 1342, carbomer copolymers,carbomer homopolymers, carbomer interpolymers, and combinations thereof.Some carbomers are available commercially as Carbopol® 934P NF polymer,Carbopol® 971P NF polymer, and Carbopolo 974P NF polymer.

Non-limiting examples of polymethacrylates can include ammoniomethacrylate copolymer, basic butylated methacrylate copolymer,methacrylic acid-methyl methacrylate copolymer (1:1), methacrylicacid-ethyl acrylate copolymer (1:1), methacrylic acid-ethyl acrylatecopolymer (1:1), methacrylic acid-methyl methacrylate copolymer (1:2),polyacrylate dispersion 30%, methacrylic acid copolymer, aminomethacrylate copolymer, ammonio methacrylate copolymer, ammoniomethacrylate copolymer dispersion, ethyl acrylate and methylmethacrylate copolymer, and combinations thereof. Some polymethacrylatesare available commercially as Eudragit® E 12.5, Eudragit® E 100,Eudragit® E PO, Eudragit® L 12.5 P, Eudragit® L 12.5, Eudragit® L 100,Eudragit® L 100-55, Eudragit® L 30 D-55, Eudragit® S 12.5 P, Eudragit® S12.5, Eudragit® S 100, Eudragit® FS 30 D, Eudragit® RL 12.5, Eudragit®RL 100, Eudragit® RL PO, Eudragit® RL 30 D, Eudragit® RS 12.5, Eudragit®RS 100, Eudragit® RS PO, Eudragit® RS 30 D, Eudragit® NE 30 D, Eudragit®NE 40 D, Eudragit® NM 30 D, Eastacryl™ 30 D, Kollicoat® MAE 30 DP,Kollicoat® MAE 100 P, Acryl-EZE®, Acryl-EZE® 93 A, and Acryl-EZE® MP.

Non-limiting examples of other synthetic polymers can include polyvinylalcohol, carboxyvinyl polymers, polyvinyl pyrrolidones, polyethyleneoxide, polyoxyethylene, and combinations thereof.

The polymer of the present invention can be selected such that itsweight average molecular weight is from about 20,000 Daltons (Da) toabout 10,000,000 Da, from about 100,000 Da to about 5,000,000 Da, fromabout 500,000 Da to about 4,000,000 Da, or from about 1,000,000 Da toabout 3,000,000 Da. The weight average molecular weight is computed bysumming the weight average molecular weight of each nonwoven web formingmaterial raw material multiplied by their respective relative weightpercentages by weight of the total weight of polymers present within thefilament.

The polymer can be polyvinyl alcohol with a weight average molecularweight from about 10,000 Da to about 250,000 Da, in another embodimentfrom about 15,000 Da to about 200,000 Da, and in another embodiment fromabout 20,000 Da to about 150,000 Da.

The polyvinyl alcohol can have a degree of hydrolysis of from about 60%to 100%, from about 65% to about 85%, less than 85%, from about 70% toabout 80%, or from about 65% to about 95%.

The polymer can be selected from the group consisting of alginates,starch-based polymers, native starches, modified starches, andcombinations thereof with a weight average molecular weight from about1,000,000 Da to about 6,000,000 Da, from about 1,500,000 Da to about5,000,000 Da, or from about 2,000,000 Da to about 4,000,000 Da.

The polymer can be selected from the group consisting of polyvinylalcohol, pullulan, pectin, corn starch, modified corn starch,hydroxypropyl methylcellulose, and combinations thereof.

The fibrous composition can comprise from about 0.1% to about 50%, fromabout 5% to about 40%, from about 15% to about 35, from about 20% toabout 30%, or from about 15% to about 30% of a polymer, by weight of thefibrous composition.

The nonfibrous composition can comprise from about 0.1% to about 50%,from about 5% to about 40%, from about 15% to about 35, from about 20%to about 30%, or from about 15% to about 30% of a polymer, by weight ofthe nonfibrous composition or the oral care composition.

Plasticizer

The oral care composition can comprise a plasticizer. Non-limitingexamples of plasticizers can include polyols, polycarboxylic acids,polyesters, other suitable plasticizers, and combinations thereof.

Non-limiting examples of polycarboxylic acids can include citric acid,succinic acid, and combinations thereof.

Non-limiting examples of polyesters can include glycerol triacetate,diethyl phthalate, triethyl citrate, tributyl citrate, acetyl triethylcitrate, acetyl tributyl citrate, and combinations thereof.

Non-limiting examples of other suitable plasticizers of the presentinvention include, but are not limited to, alkyl and allyl phthalates;lactates (e.g., sodium, ammonium and potassium salts); lactic acid;soluble collagen; modified protein; monosodium L-glutamate; proteins andamino acids such as glutamic acid, aspartic acid, and lysine; hydrogenstarch hydrolysates; other low molecular weight esters (e.g., esters ofC2-C10 alcohols and acids); and any other plasticizer known to oneskilled in the art of the food, dietary supplements, and pharmaceuticalindustries; and combinations thereof.

Polyol

The oral care composition can comprise a polyol. The fibrous compositionor the nonfibrous composition can comprise a polyol. The web formingmaterial can comprise a polyol. The foam forming material can comprise apolyol. A polyol is an organic compound with more than one hydroxylfunctional groups. The polyol can comprise a sugar alcohol, anon-reducing sugar, a monosaccharide, a disaccharide, a polysaccharide,and/or combinations thereof.

Sugar alcohols are a class of polyols that can be obtained through thehydrogenation of sugar compounds with the formula (CHOH)_(m)H₂,preferably where n=2-6. Suitable sugar alcohols include ethylene glycol,glycerin, erythritol, threitol, arabitol, xylitol, ribitol, mannitol,sorbitol, galactitol, fucitol, iditol, inositol, volemitol, isomalt,maltitol, lactitol, maltomtriitol, maltotetraitol, and/or polyglycitol.

Non-reducing sugars are a class of saccharides that do not generate anycompounds containing an aldehyde functional group. Non-reducing sugarsare stable in water and do not react with weak oxidizing agents toproduce sugar alcohols.

Non-limiting examples of monosaccharides can include glucose, fructose,and combinations thereof.

Non-limiting examples of disaccharides can include sucrose, maltose,lactose, high fructose corn syrup solids, trehalose, cellobiose,gentiobiose, isomaltose, kojibiose, laminaribiose, mannobiose,melibiose, nigerose, rutinose, xylobiose, lactulose and combinationsthereof.

Non-limiting examples of trioses can include glyceraldehydes,dihydroxyacetone, and combinations thereof.

Non-limiting examples of tetroses can include erythrose, threose,erythrulose, and combinations thereof.

Non-limiting examples of pentoses can include arabinose, lyxose, ribose,xylose, ribulose, xylulose, and combinations thereof.

Non-limiting examples of hexoses can include allose, altrose, galactose,glucose, gulose, idose, mannose, talose, fructose, psicose, sorbose,tagatose, and combinations thereof.

Non-limiting examples of heptoses can include mannoheptulose,sedoheptulose, and combinations thereof.

Non-limiting examples of octoses can include octolose,2-keto-3-deoxy-manno-octonate, and combinations thereof. A non-limitingexample of nonose can include sialose.

The oral care composition can comprise from about 0.01% to about 50%,from about 0.1% to about 50%, from about 1% to about 40%, from about 2%to about 25%, from about 5% to about 15%, or from about 5% to about 10%of a polyol, by weight of the oral care composition.

Water

The oral care composition can comprise from about 0.01% to about 50%, byweight of the oral care composition of water. The oral care compositioncan comprise from about 0.01% to about 30%, from about 0.1% to about25%, from about 0.5% to about 15%, or from about 1% to about 15% ofwater, by weight of the composition. The water may be added to theformulation directly and/or may come into the composition from theinclusion of other ingredients. Preferably, the water is USP water.Alternatively, the oral care composition can comprise less than about5%, less than about 1%, less than about 0.5%, or less than about 0.01%water by weight of the total composition. The oral care composition cancomprise no added water other than the minimal amount of water incommercial products incorporated into the oral care composition or thewater incorporated under ambient conditions.

Abrasive

The oral care composition can comprise about 0.5% to 75% of an abrasiveby weight of the oral care composition. The oral care composition cancomprise from about 5% to about 60%, from about 10% to about 50%, orfrom about 15% to about 55%, or combinations thereof, of an abrasive byweight of the composition. The abrasive can be a calcium-containingabrasive, a silica abrasive, a carbonate abrasive, a phosphate abrasive,an alumina abrasive, other suitable abrasives, and/or combinationsthereof. Some abrasives may fit into several descriptive categories,such as for example calcium carbonate, which is both acalcium-containing abrasive and a carbonate abrasive.

The calcium-containing abrasive can comprise calcium carbonate,dicalcium phosphate, tricalcium phosphate, calcium orthophosphate,calcium metaphosphate, calcium polyphosphate, calcium hydroxyapatite,and combinations thereof.

The calcium-containing abrasive can comprise calcium carbonate. Thecalcium-containing abrasive can be selected from the group consisting offine ground natural chalk, ground calcium carbonate, precipitatedcalcium carbonate, and combinations thereof.

The carbonate abrasive can comprise sodium carbonate, sodiumbicarbonate, calcium carbonate, strontium carbonate, and/or combinationsthereof.

The phosphate abrasive can comprise calcium phosphate, sodiumhexametaphosphate, dicalcium phosphate, tricalcium phosphate, calciumorthophosphate, calcium metaphosphate, calcium polyphosphate, apolyphosphate, a pyrophosphate, and/or combinations thereof.

The silica abrasive can comprise fused silica, fumed silica,precipitated silica, hydrated silica, and/or combinations thereof.

The alumina abrasive can comprise polycrystalline alumina, calcinedalumina, fused alumina, levigated alumina, hydrated alumina, and/orcombinations thereof.

Other suitable abrasives include diatomaceous earth, barium sulfate,wollastonite, perlite, polymethylmethacrylate particles, tospearl, andcombinations thereof.

The abrasive can be formed within the fibrous composition, added to thesurface of the fibrous composition, or included in the nonfibrouscomposition.

Fluoride Ion Source

The oral care composition may include an effective amount of ananti-caries agent. The oral care composition can comprise a fluoride ionsource.

The fluoride ion source may be present in an amount sufficient to give asuitable fluoride ion concentration in the composition according tolocal laws and regulations, for example the anti-caries monograph at theFDA. The oral care composition can comprise from about 0.0025% to about20%, from about 0.0025% to about 10%, from about 0.01% to about 5%, orfrom about 0.0025% to about 2%, by weight of the oral care composition,of the fluoride ion source.

The fluoride ion source can be at an amount suitable to obtain atheoretical fluoride concentration of from about 200 ppm to about 10000ppm, from about 200 ppm to about 2000 ppm, from about 800 ppm to about1500 ppm, or from about 1100 ppm to about 1400 ppm as normalized to aunit-dose oral care composition by adding water.

The fluoride ion source can comprise examples of suitable fluorideion-yielding materials are disclosed in U.S. Pat. Nos. 3,535,421, and3,678,154. The fluoride ion source can comprise stannous fluoride,sodium fluoride, potassium fluoride, amine fluoride, sodiummonofluorophosphate, zinc fluoride, and/or combinations thereof.

The fluoride ion source and the metal ion source can be the samecompound, such as for example, stannous fluoride, which can generate tinions and fluoride ions. Additionally, the fluoride ion source and thetin ion source can be separate compounds, such as when the metal ionsource is stannous chloride and the fluoride ion source is sodiummonofluorophosphate or sodium fluoride.

The fluoride ion source can be formed within the fibrous composition,added to the surface of the fibrous composition, or included in thenonfibrous composition.

Metal Ion Source

The oral care composition can comprise a metal ion source. Suitablemetal ion sources include stannous ion sources, zinc ion sources, copperion sources, silver ion sources, magnesium ion sources, iron ionsources, sodium ion sources, and manganese (Mn) ion sources, and/orcombinations thereof. The metal ion source can be a soluble or asparingly soluble compound of stannous, zinc, or copper with inorganicor organic counter ions. Examples include the fluoride, chloride,chlorofluoride, acetate, hexafluorozirconate, sulfate, tartrate,gluconate, citrate, malate, glycinate, pyrophosphate, metaphosphate,oxalate, phosphate, carbonate salts and oxides of stannous, zinc, andcopper.

Stannous, zinc and copper ions are derived from the metal ion source(s)can be found in the multi-phase oral care composition an effectiveamount to provide an oral care benefit or other benefits. Stannous, zincand copper ions have been found to help in the reduction of gingivitis,plaque, sensitivity, and improved breath benefits. An effective amountis defined as from at least about 500 ppm to about 20,000 ppm metal ionof the total composition, preferably from about 2,000 ppm to about15,000 ppm. More preferably, metal ions are present in an amount fromabout 3,000 ppm to about 13,000 ppm and even more preferably from about5,000 ppm to about 10,000 ppm. This is the total amount of metal ions(stannous, zinc, copper and mixtures thereof) that is present in thecompositions for delivery to the tooth surface.

Other metal ion sources can include minerals and/or calcium containingcompounds, which can lead to remineralization, such as, for example,sodium iodide, potassium iodide, calcium chloride, calcium lactate,calcium phosphate, hydroxyapatite, fluoroapatite, amorphous calciumphosphate, crystalline calcium phosphate, sodium bicarbonate, sodiumcarbonate, calcium carbonate, oxalic acid, dipotassium oxalate,monosodium monopotassium oxalate, casein phosphopeptides, and/or caseinphosphopeptide coated hydroxy apatite.

The metal ion source may comprise a metal salt suitable for generatingmetal ions in the oral cavity. Suitable metal salts include salts ofsilver (Ag), magnesium (Mg), iron (Fe), sodium (Na), and manganese (Mn)salts, or combinations thereof. Preferred salts include, withoutlimitation, gluconates, chlorates, citrates, chlorides, fluorides, andnitrates, or combinations thereof.

The oral care composition can comprise at least about 0.005%, from about0.005% to about 10%, from about 0.01% to about 5%, from about 0.01% toabout 2%, or from about 0.1% to about 1% of a metal ion source by weightof the oral care composition. The metal ion source can be formed withinthe fibrous composition, added to the surface of the fibrouscomposition, or included in the nonfibrous composition.

Tin Ion Source

Tin ions, such as stannous ions, are used in oral care compositions todeliver benefits such as, for example, enamel care and cavityprotection. Suitable tin ion sources include stannous chloride, stannousfluoride, stannous bromide, stannous iodide, stannous acetate, stannousgluconate, stannous oxalate, stannous sulfate, stannous lactate,stannous tartrate stannous carbonate, stannic chloride, stannicfluoride, stannic iodide, stannous citrate, stannic nitrate, stannouspeptides, stannous proteins, and stannous phosphate, and combinationsthereof. Preferably, the ion source is stannous fluoride, stannouschloride, and/or combinations thereof.

The oral care compositions of the present invention may comprise a tinion source in the amount ranging from about 0.01% to about 5%, fromabout 0.05% to about 4%, from about 0.01% to about 10%, or from about0.075% to about 3%. The tin ion source can be formed within the fibrouscomposition, added to the surface of the fibrous composition, orincluded in the nonfibrous composition.

Zinc Ion Source

The oral care composition may comprise from about 0.01% to about 5%,from about 0.2% to about 2%, or from about 0.01% to about 10%, by weightof the oral care composition, of a zinc ion source. The zinc ion sourcecan be selected from the group consisting of zinc citrate, zincchloride, zinc sulfate, zinc gluconate, zinc lactate, zinc phosphate,zinc arginine, zinc fluoride, zinc iodide, zinc carbonate, andcombinations thereof. More preferably, the zinc ion source is selectedfrom zinc citrate, zinc gluconate, zinc lactate, and combinationsthereof. Insoluble or sparingly soluble zinc compounds, such as zincoxide or zinc carbonate, can be used as the zinc ion source. Zinc ionsources can be soluble zinc sources such as zinc chloride or zincsulfate. Additionally, zinc ion sources can be those where the zinc isalready combined with a suitable chelating agent in the form of a saltor other complex, such as zinc citrate, zinc gluconate, zinc lactate andzinc glycinate. Other examples of zinc ion sources are zinc citrate,zinc gluconate, zinc lactate and mixtures thereof.

When insoluble and soluble zinc compounds are both present in the zincion source, the soluble zinc compound can be present at least about 50%,by weight of the total zinc ion source. The oral care compositions ofthe present invention may optionally also include other antibacterialagents, preferably present in an amount of from about 0.035% or more,from about 0.05% to about 2%, from about 0.1% to about 1%, by weight ofthe oral care composition. Examples of these other anti-bacterial agentsmay include non-cationic anti-bacterial agents such as, for example,halogenated diphenyl ethers, phenolic compounds including phenol and itshomologs, mono and poly-alkyl and aromatic halophenols, resorcinol andits derivatives, xylitol, bisphenolic compounds and halogenatedsalicylanilides, benzoic esters, and halogenated carbanilidies. Otheruseful anti-bacterial agents are enzymes, including endoglycosidase,papain, dextranase, mutanase, and combinations thereof. In anotherexample, the other anti-bacterial agent can include triclosan(5-chloro-2-(2,4-dichlorophenoxy)phenol).

The zinc ion source can be formed within the fibrous composition, addedto the surface of the fibrous composition, or included in the nonfibrouscomposition.

Copper Ion Source

The oral care composition can comprise from about 0.01% to about 5%,from about 0.2% to about 2%, or from about 0.01% to about 10%, by weightof the oral care composition, of a copper ion source. The copper ionsource can be selected from the group consisting of copper gluconate,copper citrate, copper fluoride, copper iodide, copper bromide, copperpeptides, copper sulfate, copper arginine, copper carbonate, andcombinations thereof. Copper salts can be in any possible oxidationstate, including, for example, copper(I) or copper(II) salts. The copperion source can be formed within the fibrous composition, added to thesurface of the fibrous composition, or included in the nonfibrouscomposition.

Calcium Ion Source

The oral care composition can comprise a calcium ion source. The calciumion source can comprise a calcium salt, such as, for example, calciumchloride, and/or a calcium-containing abrasive, as described herein.

The calcium compound can comprise any suitable soluble calcium salt,such as for example, calcium chloride, calcium carbonate, calciumbicarbonate, calcium hydroxide, calcium lactate, calcium citrate,calcium phosphate, and combinations thereof.

The oral care composition can comprise from about 0.01% to about 10%,from about 1% to about 50%, from about 10% to about 50%, or from about1% to about 30%, by weight of the oral care composition of a calcium ionsource.

Surfactants

The oral care composition can comprise one or more surfactants. Thefibrous composition can comprise one or more surfactants. The nonfibrouscomposition can comprise one or more surfactants. The one or moresurfactants may be selected from anionic, nonionic, amphoteric,zwitterionic, cationic surfactants, or combinations thereof.

The oral care composition may include one or more surfactants at a levelof from about 0.01% to about 20%, from about 1% to about 15%, from about0.1% to about 15%, from about 5% to about 15%, or greater than about5%%, by weight of the composition.

Suitable anionic surfactants include, for example, the water solublesalts of alkyl sulfates having from 8 to 20 carbon atoms in the alkylradical and the water-soluble salts of sulfonated monoglycerides offatty acids having from 8 to 20 carbon atoms. Sodium lauryl sulfate(SLS) and sodium coconut monoglyceride sulfonates are examples ofanionic surfactants of this type. Other suitable anionic surfactantsinclude sarcosinates, such as sodium lauroyl sarcosinate, taurates,sodium lauryl sulfoacetate, sodium lauroyl isethionate, sodium laurethcarboxylate, and sodium dodecyl benzene sulfonate. Combinations ofanionic surfactants can also be employed.

Another suitable class of anionic surfactants are alkyl phosphates. Thesurface active organophosphate agents can have a strong affinity forenamel surface and have sufficient surface binding propensity to desorbpellicle proteins and remain affixed to enamel surfaces. Suitableexamples of organophosphate compounds include mono-, di- or triestersrepresented by the general structure below wherein Z₁, Z₂, or Z₃ may beidentical or different with at least one being an organic moiety. Z₁,Z₂, or Z₃ can be selected from linear or branched, alkyl or alkenylgroup of from 1 to 22 carbon atoms, optionally substituted by one ormore phosphate groups; alkoxylated alkyl or alkenyl, (poly)saccharide,polyol or polyether group.

Some other agents include alkyl or alkenyl phosphate esters representedby the following structure:

wherein R₁ represents a linear or branched, alkyl or alkenyl group offrom 6 to 22 carbon atoms, optionally substituted by one or morephosphate groups; n and m, are individually and separately, 2 to 4, anda and b, individually and separately, are 0 to 20; Z and Z may beidentical or different, each represents hydrogen, alkali metal,ammonium, protonated alkyl amine or protonated functional alkylamine,such as analkanolamine, or a R—(OCH2)(OCH)—group. Examples of suitableagents include alkyl and alkyl (poly)alkoxy phosphates such as laurylphosphate; PPGS ceteareth-10 phosphate; laureth-1 phosphate; laureth-3phosphate; laureth-9 phosphate; trilaureth-4 phosphate; C₁₂₋₁₈ PEG 9phosphate: and sodium dilaureth-10 phosphate. The alkyl phosphate can bepolymeric. Examples of polymeric alkyl phosphates include thosecontaining repeating alkoxy groups as the polymeric portion, inparticular 3 or more ethoxy, propoxy isopropoxy or butoxy groups.

Other suitable surfactants are sarcosinates, isethionates and taurates,especially their alkali metal or ammonium salts. Examples include:lauroyl sarcosinate, myristoyl sarcosinate, palmitoyl sarcosinate,stearoyl sarcosinate oleoyl sarcosinate, or combinations thereof.

Zwitterionic or amphoteric Surfactants useful herein include derivativesof aliphatic quaternary ammonium, phosphonium, and Sulfonium compounds,in which the aliphatic radicals can be straight chain or branched, andone of the aliphatic substituents contains from 8 to 18 carbon atoms andone contains an anionic water-solubilizing group, e.g., carboxy,sulfonate, sulfate, phosphate or phosphonate. Suitable betainesurfactants are disclosed in U.S. Pat. No. 5,180,577. Typical alkyldimethyl betaines include decyl betaine or2-(N-decyl-N,N-dimethylammonio) acetate, coco-betaine or2-(N-coco-N,N-dimethyl ammonio)acetate, myristyl betaine, palmitylbetaine, lauryl betaine, cetyl betaine, cetyl betaine, stearyl betaine,etc. The amidobetaines can be exemplified by cocoamidoethyl betaine,cocoamidopropyl betaine (CADB), and lauramidopropyl betaine.

Cationic surfactants useful in the present invention include, forexample, derivatives of quaternary ammonium compounds having one longalkyl chain containing from 8 to 18 carbon atoms such as lauryltrimethylammonium chloride; cetyl pyridinium chloride; cetyltrimethyl-ammonium bromide; cetyl pyridinium fluoride or combinationsthereof.

Nonionic surfactants that can be used in the compositions of the presentinvention include, for example, compounds produced by the condensationof alkylene oxide groups (hydrophilic in nature) with an organichydrophobic compound which may be aliphatic or alkylaromatic in nature.Examples of suitable nonionic surfactants can include the Pluronics®which are poloxamers, polyethylene oxide condensates of alkyl phenols,products derived from the condensation of ethylene oxide with thereaction product of propylene oxide and ethylene diamine, ethylene oxidecondensates of aliphatic alcohols, long chain tertiary amine oxides,long chain tertiary phosphine oxides, long chain dialkyl sulfoxides andcombinations of such materials.

The one or more surfactants can also include one or more naturalsurfactants. Natural surfactants can include surfactants that arederived from natural products and/or surfactants that are minimally ornot processed. Natural surfactants can include hydrogenated,non-hydrogenated, or partially hydrogenated vegetable oils, olus oil,Passiflora incarnata oil, candelilla cera, coco-caprylate, caprate,dicaprylyl ether, lauryl alcohol, myristyl myristate, dicaprylyl ether,caprylic acid, caprylic ester, octyl decanoate, octyl octanoate,undecane, tridecane, decyl oleate, oleic acid decylester, cetylpalmitate, stearic acid, palmitic acid, glyceryl stearate, hydrogenated,non-hydrogenated, or partially hydrogenated vegetable glycerides,Polyglyceryl-2 dipolyhydroxystearate, cetearyl alcohol, sucrosepolystearate, glycerin, octadodecanol, hydrolyzed, partially hydrolyzed,or non-hydrolyzed vegetable protein, hydrolyzed, partially hydrolyzed,or non-hydrolyzed wheat protein hydrolysate, polyglyceryl-3diisostearate, glyceryl oleate, myristyl alcohol, cetyl alcohol, sodiumcetearyl sulfate, cetearyl alcohol, glyceryl laurate, caprictriglyceride, coco-glycerides, lectithin, dicaprylyl ether, xanthan gum,sodium coco-sulfate, ammonium lauryl sulfate, sodium cocoyl sulfate,sodium cocoyl glutamate, polyalkylglucosides, such as decyl glucoside,cetearyl glucoside, cetyl stearyl polyglucoside, coco-glucoside, andlauryl glucoside, and/or combinations thereof. Natural surfactants caninclude any of the Natrue ingredients marketed by BASF, such as, forexample, CegeSoft®, Cetiol®, Cutina®, Dehymuls®, Emulgade®, Emulgin®,Eutanol®, Gluadin®, Lameform®, LameSoft®, Lanette®, Monomuls®, Myritol®,Plantacare®, Plantaquat®, Platasil®, Rheocare®, Sulfopon®, Texapon®,and/or combinations thereof.

The surfactant can be formed within the fibrous composition, added tothe surface of the fibrous composition, and/or included in thenonfibrous composition. The surfactant formed within the fibrouscomposition can be at a level from about 10% to about 50%, from about20% to about 40%, from about 25% to about 40%, or from about 30% toabout 40% by weight of the fibrous composition.

The oral care composition can comprise one or more surfactants. The oralcare composition can comprise an anionic surfactant, a cationicsurfactant, a nonionic surfactant, and/or a zwitterionic surfactant.

The oral care composition can comprise from about 0.1% to about 10%,from about 0.1% to about 8%, from about 5% to about 8%, from about 4% toabout 9%, or from about 3% to about 10% of an anionic surfactant,cationic surfactant, and/or nonionic surfactant by weight of thecomposition.

The oral care composition can comprise from about 0.01% to about 20%,from about 0.01% to about 10%, from about 0.1% to about 1%, from about0.01% to about 1%, from about 0.01% to about 0.5%, or from about 0.1% toabout 0.2% of a zwitterionic surfactant by weight of the composition.

PEG

The oral care composition may comprise polyethylene glycol (PEG), ofvarious weight percentages of the composition as well as various rangesof average molecular weights. The compositions can have from about 0.1%to about 40%, from about 1% to about 35%, from about 5% to about 30%,from about 15% to about 25%, from about 1% to about 40%, from about 10%to about 30%, from about 15% to about 20%, from about 0.1% to about 30%,or from about 15% to about 30% of PEG by weight of the composition. ThePEG can have a range of average molecular weight from about 100 Daltonsto about 1600 Daltons, from about 200 to about 1000, from about 400 toabout 800, from about 500 to about 700 Daltons, or combinations thereof.PEG is a water soluble linear polymer formed by the addition reaction ofethylene oxide to an ethylene glycol equivalent having the generalformula: H—(OCH₂CH₂)_(n)—OH. One supplier of PEG is Dow Chemical Companyunder the brandname of CARBOWAX™.

PEG can be formed within the fibrous composition, added to the surfaceof the fibrous composition, or included in the nonfibrous composition.PEG included in the nonfibrous composition can be at a level from about10% to about 50%, from about 15% to about 40%, from about 5% to about35%, or from about 15% to about 30% by weight of the nonfibrouscomposition. The PEG, when used as a solvent for the nonfibrouscomposition, can be anhydrous to prevent reactivity between componentsdispersed or dissolved within the PEG.

Polyphosphates

The oral care composition can comprise a polyphosphate source. Apolyphosphate source can comprise one or more polyphosphate molecules.Polyphosphates are a class of materials obtained by the dehydration andcondensation of orthophosphate to yield linear and cyclic polyphosphatesof varying chain lengths. Thus, polyphosphate molecules are generallyidentified with an average number (n) of polyphosphate molecules, asdescribed below. A polyphosphate is generally understood to consist oftwo or more phosphate molecules arranged primarily in a linearconfiguration, although some cyclic derivatives may be present.

Preferred polyphosphates are those having an average of two or morephosphate groups so that surface adsorption at effective concentrationsproduces sufficient non-bound phosphate functions, which enhance theanionic surface charge as well as hydrophilic character of the surfaces.Preferred in this invention are the linear polyphosphates having theformula: XO(XPO₃)_(n)X, wherein X is sodium, potassium, ammonium, or anyother alkali metal cations and n averages from about 2 to about 21. Thepolyphosphate source can also include alkali earth metal polyphosphatesalts, and specifically calcium polyphosphate salts, such as calciumpyrophosphate, due to the ability to separate calcium ions from otherreactive components, such as fluoride ion sources.

Some examples of suitable polyphosphate molecules include, for example,pyrophosphate (n=2), tripolyphosphate (n=3), tetrapolyphosphate (n=4),sodaphos polyphosphate (n=6), hexaphos polyphosphate (n=13), benephospolyphosphate (n=14), hexametaphosphate (n=21), which is also known asGlass H. Polyphosphates can include those polyphosphate compoundsmanufactured by FMC Corporation, ICL Performance Products, and/orAstaris.

The oral care composition can comprise from about 0.01% to about 15%,from about 0.1% to about 10%, from about 0.5% to about 5%, from about 1to about 20%, or about 10% or less, by weight of the oral carecomposition, of the polyphosphate source.

Extensional Aid

The oral care composition can comprise an extensional aid. Non-limitingexamples of extensional aids can include polymers, other extensionalaids, and combinations thereof.

The extensional aids can have a weight average molecular weight of atleast about 500,000 Da. The weight average molecular weight of theextensional aid can be from about 500,000 to about 25,000,000, fromabout 800,000 to about 22,000,000, from about 1,000,000 to about20,000,000, or from about 2,000,000 to about 15,000,000. The highmolecular weight extensional aids are preferred in some embodiments ofthe invention due to the ability to increase extensional melt viscosityand reducing melt fracture.

The extensional aid, when used in meltblowing, can be added to thecomposition of the present invention in an amount effective to visiblyreduce the melt fracture and capillary breakage of filaments during thespinning process such that substantially continuous filaments havingrelatively consistent diameter can be melt spun. Regardless of theprocess employed to produce filaments, the extensional aids, when used,can be present from about 0.001% to about 10%, by weight on a dryfilament basis, from about 0.005 to about 5%, by weight on a dryfilament basis, from about 0.01 to about 1%, by weight on a dry filamentbasis, or from about 0.05% to about 0.5%, by weight on a dry filamentbasis.

Non-limiting examples of polymers that can optionally be used asextensional aids can include alginates, carrageenans, pectin, chitin,guar gum, xanthum gum, agar, gum arabic, karaya gum, tragacanth gum,locust bean gum, alkylcellulose, hydroxyalkylcellulose,carboxyalkylcellulose, and mixtures thereof.

Nonlimiting examples of other extensional aids can include carboxylmodified polyacrylamide, polyacrylic acid, polymethacrylic acid,polyvinyl alcohol, polyvinylacetate, polyvinylpyrrolidone, polyethylenevinyl acetate, polyethyleneimine, polyamides, polyalkylene oxidesincluding polyethylene oxide, polypropylene oxide, polyethylenepropyleneoxide, and mixtures thereof.

Aesthetic Agents

The oral care composition can optionally comprise one or more aestheticagents. The one or more aesthetic agents can be selected from the groupconsisting of flavors, colorants, sensates, sweeteners, salivationagents, and combinations thereof. All aesthetic agents can be presentfrom about 0.001% to about 60%, by weight of the oral care composition,from about 0.005% to about 50%, by weight of the oral care composition,about 0.05% to about 40%, by weight of the oral care composition, orfrom about 0.1% to about 35%, by weight of the oral care composition.

Aesthetic agents can be formed within the fibrous composition, added tothe surface of the fibrous composition, or included in the nonfibrouscomposition.

Flavors

The oral care composition can optionally include one or more flavors.Non-limiting examples of flavors that can be used in the presentinvention can include natural flavoring agents, artificial flavoringagents, artificial extracts, natural extracts and combination thereof.Non-limiting examples of flavors can include vanilla, honey, lemon,lemon honey, cherry vanilla, peach, honey ginger, chamomile, cherry,cherry cream, mint, vanilla mint, dark berry, black berry, raspberry,peppermint, spearmint, honey peach, acai berry, cranberry, honeycranberry, tropical fruit, dragon fruit, wolf berry, red stem mint,pomegranate, black current, strawberry, lemon, lime, peach ginger,orange, orange cream, cream sickle, apricot, anethole, ginger, jackfruit, star fruit, blueberry, fruit punch, lemon grass, chamomile lemongrass, lavender, banana, strawberry banana, grape, blue raspberry, lemonlime, coffee, espresso, cappuccino, honey, wintergreen mint, bubble gum,tart honey lemon, sour lemon, green apple, boysenberry, rhubarb,strawberry rhubarb, persimmon, green tea, black tea, red tea, white tea,honey lime, cherry lime, apple, tangerine, grapefruit, kiwi, pear,vanillin, ethyl vanillin, maltol, ethyl-maltol, pumpkin, carrot cake,white chocolate raspberry, chocolate, white chocolate, milk chocolate,dark chocolate, chocolate marshmallow, apple pie, cinnamon, hazelnut,almond, cream, creme brulde, caramel, caramel nut, butter, buttertoffee, caramel toffee, aloe vera, whiskey, rum, cocoa, licorice,pineapple, guava, melon, watermelon, elder berry, mouth cooler,raspberries and cream, peach mango, tropical, cool berry, lemon ice,nectar, spicy nectar, tropical mango, apple butter, peanut butter,tangerine, tangerine lime, marshmallow, cotton candy, apple cider,orange chocolate, adipic acid, citral, denatonium benzoate, ethylacetate, ethyl lactate, ethyl maltol, ethylcellulose, fumaric acid,leucine, malic acid, menthol, methionine, monosodium glutamate, sodiumacetate, sodium lactate, tartaric acid, thymol, and combinationsthereof.

Flavors can be protected in an encapsulate or as a flavor crystal. Theencapsulated flavor can have a controlled or delayed release once theencapsulated flavor reaches the oral cavity. The encapsulate cancomprise a shell and a core. The flavor can be in the core of theencapsulate. The flavor can be encapsulated by any suitable means, suchas spray drying or extrusion. Encapsulated flavors can be added to thesurface of the fibrous composition, formed within the fibrouscomposition, or included in the nonfibrous composition.

Flavors can be present from about 0.05% to about 25%, by weight of theoral care composition, from about 0.01% to about 15%, by weight of theoral care composition, from about 0.2% to about 10%, by weight of theoral care composition, or from about 0.1% to about 5%, by weight of theoral care composition.

Flavors can be formed within the fibrous composition, added to thesurface of the fibrous composition, or included in the nonfibrouscomposition.

Colorants

The oral care composition can optionally include one or more colorants.The colorants can provide a visual signal when the oral care compositionis exposed to conditions of intended use. Non-limiting examplescolorants that may be used in the present invention include FD&C blue#1, FD&C blue #2, D&C blue #4, D&C blue #9, FD&C green #3, D&C green #5,D&C green #6, D&C green #8, D&C orange #4, D&C orange #5, D&C orange#10, D&C orange #11, FD&C red #3, FD&C red #4, D&C red #6, D&C red #7,D&C red #17, D&C red #21, D&C red #22, D&C red #27, D&C red #28, D&C red#30, D&C red #31, D&C red #33, D&C red #34, D&C red #36, D&C red #39,FD&C red #40, D&C violet #2, FD&C yellow #5, FD&C yellow #6, D&C yellow#7, Ext. D&C yellow #7, D&C yellow #8, D&C yellow #10, D&C yellow #11,and combinations thereof. Colorants can be present from about 0.05% toabout 2%, by weight of the oral care composition, from about 0.01% toabout 2%, by weight of the oral care composition, or from about 0.02% toabout 1.5%, by weight of the oral care composition.

Colorants can be formed within the fibrous composition, added to thesurface of the fibrous composition, or included in the nonfibrouscomposition.

Sensates

The oral care composition can optionally include one or more sensates.Non-limiting examples of sensates can include cooling sensates, warmingsensates, tingling sensates, and combinations thereof. Sensates areuseful to deliver signals to the user.

Non-limiting examples of cooling sensates can include WS-23(2-Isopropyl-N,2,3-trimethylbutyramide), WS-3(N-Ethyl-p-menthane-3-carboxamide), WS-30(1-glyceryl-p-mentane-3-carboxylate), WS-4(ethyleneglycol-p-methane-3-carboxylate), WS-14(N-t-butyl-p-menthane-3-carboxamide), WS-12(N-(4-,ethoxyphenyl)-p-menthane-3-carboxamide), WS-5(Ethyl-3-(p-menthane-3-carboxamido)acetate, Menthone glycerol ketal(sold as Frescolat® MGA by Haarmann & Reimer), (−)-Menthyl lactate (soldas Frescolat® ML by Haarmann & Reimer),(−)-Menthoxypropane-1,2-diol(sold as Coolant Agent 10 by TakasagoInternational), 3-(1-menthoxy)propane-1,2-diol,3-(1-Menthoxy)-2-methylpropane-1,2-diol, (−)-Isopulegol is sold underthe name “Coolact P®” by Takasago International, cis & transp-Menthane-3,8-diols(PMD38)—Takasago International, Questice® (menthylpyrrolidone carboxylate),(1R,3R,4S)-3-menthyl-3,6-dioxaheptanoate—Firmenich, (1R,2S,5R)-3-menthylmethoxyacetate—Firmenich, (1R,2S,5R)-3-menthyl3,6,9-trioxadecanoate—Firmenich, (1R,2S,5R)-menthyl11-hydroxy-3,6,9-trioxaundecanoate—Firmenich, (1R,2S,5R)-3-menthyl(2-hydroxyethoxy)acetate—Firmenich, Cubebol—Firmenich, Icilin also knownas AG-3-5, chemical name1-[2-hydroxyphenyl]-4-[2-nitrophenyl-]-1,2,3,6-tetrahydropyrimidine-2-one),4-methyl-3-(1-pyrrolidinyl)-2[5H]-furanone, Frescolat ML—menthyllactate, Frescolat MGA—menthone glycerin acetal, Peppermint oil,Givaudan 180, L-Monomenthyl succinate, L-monomenthyl glutarate,3-1-menthoxypropane-1,2-diol—(Coolact 10), 2-1-menthoxyethanol (Cooltact5), TK10 Coolact (3-1-Menthoxy propane-1,2-diol), Evercool 180(N-p-benzeneacetonitrile-menthane carboxamide), and combinationsthereof. Cooling sensates can be present from about 0.005% to about 10%,by weight of the oral care composition, from about 0.05% to about 7%, byweight of the oral care composition, or from about 0.01% to about 5%, byweight of the oral care composition.

Non-limiting examples of warming sensates can include TK 1000, TK 1 MM,Heatenol—Sensient Flavors, Optaheat—Symrise Flavors, Cinnamon,Polyethylene glycol, Capsicum, Capsaicin, Curry, FSI Flavors,Isobutavan, Ethanol, Glycerin, Nonivamide 60162807, Hotact VEE, Hotact 1MM, piperine, optaheat 295 832, optaheat 204 656, optaheat 200 349, andcombinations thereof. Warming sensates can be present from about 0.005%to about 60%, by weight on a dry filament basis, from about 0.05% toabout 50%, by weight on a dry filament basis, or from about 0.01% toabout 40%, by weight on a dry filament basis. Warming sensates can bepresent from about 0.005% to about 10%, by weight of the oral carecomposition, from about 0.05% to about 7%, by weight of the oral carecomposition, or from about 0.01% to about 5%, by weight of the oral carecomposition. Non-limiting examples of tingling sensates can includesichuan pepper, hydroxy alpha sanshool, citric acid, Jambu extracts,spilanthol, and combinations thereof. Tingling sensates can be presentfrom about 0.005% to about 10%, by weight on a dry filament basis or theoral care composition, from about 0.01% to about 7%, by weight on a dryfilament basis or the oral care composition, or from about 0.015% toabout 6%, by weight on a dry filament basis or the oral carecomposition.

Sensates can be formed within the fibrous composition, added to thesurface of the fibrous composition, or included in the nonfibrouscomposition.

Sweeteners

The oral care composition can optionally include one or more sweeteners.Sweeteners can be natural or artificial. Non-limiting examples ofsweeteners can include nutritive sweeteners, sugar alcohols, syntheticsweeteners, high intensity natural sweeteners, and combinations thereof.All sweeteners can be present from about 0.05% to about 60%, by weightof the oral care composition, from about 0.1% to about 50%, by weight ofthe oral care composition, or from about 1% to about 10%, by weight ofthe oral care composition.

Non-limiting examples of nutritive sweeteners can include sucrose,dextrose, glucose, fructose, lactose, tagatose, maltose, trehalose, andcombinations thereof. Nutritive sweeteners can be present from about0.1% to about 60%, by weight of the oral care composition, from about 1%to about 50%, by weight of the oral care composition, or from about 0.1%to about 10%, by weight of the oral care composition.

Non-limiting examples of sugar alcohols can include xylitol, sorbitol,mannitol, maltitol, lactitol, isomalt, erythritol, and combinationsthereof. Sugar alcohols can be present from about 0.1% to about 60%, byweight of the oral care composition, from about 0.11% to about 50%, byweight of the oral care composition, or from about 0.1% to about 10%, byweight of the oral care composition.

Non-limiting examples of synthetic sweeteners can include aspartame,acesulfame potassium, alitame, sodium saccharin, sucralose, neotame,cyclamate, and combinations thereof. Synthetic sweeteners can be presentfrom about 0.05% to about 10% by weight of the oral care composition,from about 0.1% to about 5%, by weight of the oral care composition, orfrom about 0.25% to about 4%, by weight of the oral care composition.

Non-limiting examples of high intensity natural sweeteners can includeneohesperidin dihydrochalcone, stevioside, rebaudioside A, rebaudiosideC, dulcoside, monoammonium glycrrhizinate, thaumatin, and combinationsthereof. High intensity natural sweeteners can be present from about0.05% to about 10% by weight of the oral care composition, from about0.1% to about 5%, by weight of the oral care composition, or from about0.25% to about 4%, by weight of the oral care composition.

Sweeteners can be formed within the nonwoven web, added to the surfaceof the nonwoven web, or included in the nonfibrous composition.

Salivation Agents

The oral care composition can optionally include one or more salivationagents. Non-limiting examples of salivation agents include formula (I):

wherein R₁ represents C1-C2 n-alkyl; R₂ is 2-methyl-1-propyl and R₃ ishydrogen, or R₂ and R₃ taken together is a moiety (designated by thedashed lines) having the formula —(CH₂)_(n)— wherein n is 4 or 5, andcombinations thereof.

The salivating agent can comprise a material wherein R₂ is2-methyl-1-propyl and R₃ is hydrogen or the salivating agent cancomprise a material wherein R₁ is C1 n-alkyl, R₂ is 2-methyl-1-propyland R₃ is hydrogen. The salivating agent can comprise trans-pellitorin,a chemical having a structure according to formula (II):

The salivation agent can include sodium bicarbonate, sodium chloride,trans pelitorin, pilocarpine, citrate, and combinations thereof.Salivation agents can be present from about 1% to about 60%, from about1% to about 50%, or from about 1% to about 40%, by weight of the oralcare composition. Additionally, salivation agents can be present fromabout 0.005% to about 10%, by weight of the oral care composition, fromabout 0.01% to about 7%, by weight of the oral care composition, or fromabout 0.015% to about 6%, by weight of the oral care composition.

Salivation agents can be formed within the fibrous composition, added tothe surface of the fibrous composition, or included in the nonfibrouscomposition.

Thickening Agent

The oral care compositions herein may include one or more thickeningagents. A thickening agent may be used in an amount from about 0.01% toabout 15%, or from about 0.1% to about 10%, or from about 0.1% to about5%, by weight of the oral care composition. Non-limiting examples mayinclude those described in US 2008/0081023 A1 at paragraphs 134 to 137,and the references cited therein.

The oral care composition can comprise a linear sulfated polysaccharideas a thickening agent. Carrageenans or carrageenins are one example of alinear sulfated polysaccharide. Generally, carrageenans can vary basedupon the degree of sulfation that includes: Kappa-carrageenan,Iota-carrageenan, and Lambda-carrageenan. Combinations of carrageenanscan be used. The oral care composition can contain from about 0.1% toabout 3%, of a linear sulfated polysaccharides by weight of the oralcare composition, from about 0.5% to about 2%, from about 0.6% to about1.8%, or combinations thereof.

The oral care composition can comprise a silica agent, preferably athickening silica obtained from sodium silicate solution bydestabilizing with acid as to yield very fine particles. Onecommercially available example is ZEODENT® branded silicas from HuberEngineered Materials (e.g., ZEODENT® 103, 124, 113 115, 163, 165, 167).The oral care composition can include from about 0.5% to about 5% byweight of the oral care composition of a silica agent, preferably fromabout 1% to about 4%, alternatively from about 1.5% to about 3.5%,alternatively from about 2% to about 3%, alternatively from about 2% toabout 5% alternatively from about 1% to 3%, alternatively combinationsthereof.

The thickening agent can comprise a carboxymethyl cellulose (“CMC”). CMCis prepared from cellulose by treatment with alkali andmonochloro-acetic acid or its sodium salt. Different varieties arecommercially characterized by viscosity. One commercially availableexample is Aqualon™ branded CMC from Ashland Special Ingredients (e.g.,Aqualon™ 7H3SF; Aqualon™ 9M3SF Aqualon™ TM9A; Aqualon™ TM12A). Thethickening agent can contain from about 0.1% to about 3% of a CMC byweight of the oral care composition, preferably from about 0.5% to about2%, alternatively from about 0.6% to about 1.8%, alternativelycombinations thereof.

Thickening agents can be formed within the fibrous composition, added tothe surface of the fibrous composition, or included in the nonfibrouscomposition.

Chelants

The oral care compositions of the present invention can comprise one ormore chelants, also known as chelating agents. The term “chelant”, asused herein means a bi- or multidentate ligand having at least twogroups capable of binding to metal ions and preferably other divalent orpolyvalent metal ions and which, at least as part of a chelant mixture,is capable of solubilizing tin ions or other optional metal ions withinthe oral care composition. Groups capable of binding to metal ionsinclude carboxyl, hydroxl, and amine groups.

Suitable chelants herein include C₂-C₆ dicarboxylic and tricarboxylicacids, such as succinic acid, malic acid, tartaric acid and citric acid;C₃-C₆ monocarboxylic acids substituted with hydroxyl, such as gluconicacid; picolinic acid; amino acids such as glycine; salts thereof andmixtures thereof. The chelants can also be a polymer or copolymer inwhich the chelating ligands are on the same or adjacent monomer

Preferred chelant polymers are polyacids selected from the groupconsisting of a homopolymer of a monomer, a co-polymer of two or moredifferent monomers, and a combination thereof wherein the monomer or atleast one of the two or more different monomers is selected from thegroup consisting of acrylic acid, methacrylic acid, itaconic acid,maleic acid, glutaconic acid, aconitic acid, citraconic acid, mesaconicacid, fumaric acid and tiglic acid. Particularly preferred is amethylvinylether/maleic acid (PVM/MA) copolymer. Other useful chelantsinclude polyphosphates, as discussed herein.

Preferred organic acid chelants herein comprise citrate, malate,tatirate, gluconate, succinate, lactate, malonate, maleate, and mixturesthereof, whether added in their free acid or salt forms.

The oral care compositions of the present invention can have low levelsof chelants because metals ions can require less stabilization ifintroduced in a fibrous composition, a nonfibrous composition, orphysically separated from other reactive components of the oral carecomposition, which can be added in a separate web layer or in thenonfibrous composition. The oral care composition can have less thanabout 5%, less than about 1%, less than about 0.5%, less than 0.1%, lessthan about 0.01%, or 0% of chelants, by weight of the oral carecomposition. Chelants can be formed within the fibrous composition,added to the surface of the fibrous composition, or included in thenonfibrous composition.

Whitening Agents

The oral care composition may further comprise from about 0.1% to about10%, from about 0.2% to about 5%, from about 1% to about 5%, or fromabout 1% to about 15%, by weight of the total oral care composition of awhitening agent. The whitening agent can be a compound suitable forwhitening at least one tooth in the oral cavity. The whitening agent mayinclude peroxides, metal chlorites, perborates, percarbonates,peroxyacids, persulfates, and combinations thereof. Suitable peroxidesinclude solid peroxides, urea peroxide, calcium peroxide, benzoylperoxide, sodium peroxide, barium peroxide, inorganic peroxides,hydroperoxides, organic peroxides, and mixtures thereof. Suitable metalchlorites include calcium chlorite, barium chlorite, magnesium chlorite,lithium chlorite, sodium chlorite, and potassium chlorite. Othersuitable whitening agents include sodium persulfate, potassiumpersulfate, peroxydone, 6-phthalimido peroxy hexanoic acid,Pthalamidoperoxycaproic acid, or mixtures thereof.

Whitening agents can be reactive with other components of oral carecompositions, thus, can be separated from other components using theassembly design described herein. Whitening agents can be formed withinthe fibrous composition, added to the surface of the fibrouscomposition, or included in the nonfibrous composition.

Bioactive Materials

The oral care composition can also include bioactive materials suitablefor the remineralization of a tooth. Suitable bioactive materialsinclude bioactive glasses, Novamin™, Recaldent™ hydroxyapatite, aminoacids, such as, for example, arginine, citrulline, glycine, lysine, orhistidine, or combinations thereof. Other suitable bioactive materialsinclude any calcium phosphate compound.

Other suitable bioactive materials include compounds comprising acalcium source and a phosphate source.

Bioactive glasses are comprising calcium and/or phosphate which can bepresent in a proportion that is similar to hydroxyapatite. These glassescan bond to the tissue and are biocompatible. Bioactive glasses caninclude a phosphopeptide, a calcium source, phosphate source, a silicasource, a sodium source, and/or combinations thereof.

The oral care composition can comprise from about 0.01% to about 20%,from about 0.1% to about 10%, or from about 1% to about 10% of abioactive material by weight of the oral care composition.

Bioactive materials can be formed within the fibrous composition, addedto the surface of the fibrous composition, or included in the nonfibrouscomposition.

Nonfibrous Compositions

The components described herein can optionally be present, at leastpartially, as a nonfibrous composition. The nonfibrous composition canbe between two or more web layers, folded inside at least one web layer,rolled inside at least web layer, or wrapped in at least one web layer.At least a portion of the nonfibrous composition can contact the surfaceof a fibrous composition. The nonfibrous composition can be liquid,solid, aqueous, and/or combinations thereof.

The nonfibrous composition may comprise an oral care active, aestheticagent, abrasive, fluoride ion source, web forming material, metal ionsource, polyphosphate, chelant, anti-calculus agent, thickening agent,polymer, surfactant, bioactive material and/or combinations thereof.

The nonfibrous composition can be from about 10% to about 90%, fromabout 20% to about 85%, from about 30% to about 80%, from about 40% toabout 75%, from about 50% to about 80%, from about 50% to about 90%, orfrom about 60% to about 80% by weight of the oral care composition.

The density of the nonfibrous composition can be from about 0.05 g/cm³to about 5 g/cm³, from about 0.75 g/cm³ to about 1.9 g/cm³, from about 1g/cm³ to about 1.75 g/cm³, or from about 1.4 g/cm³ to about 1.8 g/cm³.

Coating Composition

The components described herein can optionally be present, at leastpartially, as a coating composition. The coating composition can beapplied to the fibrous composition, web, or the oral care composition.The coating composition at least partially covers or covers an outersurface of the fibrous composition or the web. The coating compositioncan cover an outer surface of the oral care composition putting thecoating composition in position to immediately contact the targetsurface (e.g. saliva in the mouth) during use for the release of theoral care active(s) and/or aesthetic agent(s).

The coating composition of the present invention may comprise one ormore oral care actives as defined herein. The coating composition of thepresent invention may comprise one or more aesthetic agents as definedherein.

The fibrous composition, web, or oral care composition may comprise oneor more oral care actives which can be the same or different from theoral care active present in the coating composition. The fibrouscomposition, web, or oral care composition can comprise a delayeddelivery, an extended delivery oral care active, and/or a targeteddelivery oral care active and the coating composition comprises animmediate delivery oral care active. The fibrous composition, web, ororal care composition can comprise one or more aesthetic agents whichcan be the same or different from the aesthetic agent in the coatingcomposition.

The coating composition can also be entrapped within the fibrouscomposition or the web. Thus, the particles of the coating compositioncan fit within the void between the fibers or filaments when formed intoa web using any suitable means.

Releasable Components

Oral care actives, aesthetic agents, or other components in the oralcare composition can be designed to be releasable upon a suitabletriggering condition. The releasable components can be releasable on thesame or a different triggering condition. For example, a flavorencapsulate can be releasable upon a shear rate associated with a userbrushing at least one tooth. A fluoride ion source can be releasableupon contact with water. This can allow for oral care actives oraesthetic agents to be released at a designable time. For example, aflavor can be released 1 seconds after brushing while a colorant can bereleasable after a user has brushed for two minutes to indicate asuitable brushing time has passed. Aesthetic agents or oral care activescan be delivered sequentially or simultaneous with other aestheticagents or oral care actives.

Graphics

Graphics can be printed directly on the oral care compositions. Suitablegraphics include graphics to match flavors, graphics of sports teamslogos or names, graphics to match directions for use, such as use at aparticular time of day, after consuming a certain food or drink, or thetype of brush to use, marketing material, colors, designs, logos,graphics depicting fictional and nonfictional characters, graphics tiedto a consumer benefit, flags, phrases, catch phrases, motivationalquotes, branding material, company information, ingredient lists,animals, or other suitable graphics to convey information directly onthe oral care compositions. Graphics can be printed on each side of theoral care composition. Graphics can be the same or different on eachside of the oral care composition.

Dissolution Time

The oral care compositions of the present invention can be described bytheir dissolution times. The oral care compositions of the presentinvention dissolve much quicker than a comparable paste dentifrice. Oralcare compositions comprising a fibrous composition of the presentinvention can have a total dissolution time according to the dissolutionmethod, as described herein, of less about 1000 seconds, less than about750 seconds, less than about 500 seconds, less than about 250 seconds,from about 50 seconds to about 250 seconds, or from about 50 seconds toabout 500 seconds per dose of oral care composition. Foam compositionsof the present invention can have a total dissolution time according tothe dissolution method described herein of less than about 50 seconds,less than about 30 seconds, or less than about 20 seconds per dose ofthe foam composition. Comparable dentifrice paste formulations havedissolution times of greater than 1000 seconds which is not suitable fora unit-dose oral care composition that needs to dissolve upon contactwith moisture in the oral cavity.

Fluoride Uptake

The oral care compositions, as described herein, can be describedaccording its average fluoride uptake by HAP dissolution. The oral carecompositions of the present invention have a higher average F uptakedespite also comprising components that are typically avoided orcarefully avoided due to reactivity with fluoride ions. For example, theoral care compositions can have an average fluoride uptake of at least1000 ppm, at least 1500 ppm, or at least 2000 ppm despite comprising afluoride ion source and a calcium ion source, which can react to formprecipitated calcium fluoride prior to use by a consumer. The oral carecompositions, as described herein, physically separate the fluoride ionsource from the calcium ion source in a different nonwoven web layers,in separate portions, in separate compositions of the oral carecompositions, or in a soluble solid phase. The physical separation ofthese components have been previously difficult to achieve. Unit-doseoral care compositions, such as pouches, solid foams, or soluble fibrouscompositions, provide the chassis that can physically separate fluorideions from calcium ions during storage, but also allows them to becombinable upon dissolution and/or disintegration in the oral cavity.

Tin Ion Uptake

The oral care compositions, as described herein, can be describedaccording its average tin ion uptake by HAP dissolution. The oral carecompositions of the present invention have a higher average Sn uptakedespite also comprising components that are typically avoided orcarefully formulated due to reactivity with tin ions. For example, theoral care compositions can have an average tin ion uptake of at least5000 ppm, at least 10000 ppm, or at least 20000 ppm despite comprising atin ion source and a polyphosphate, silica abrasive, etc., which canreact to form tin complexes that low the tin ion availability prior touse by a consumer. The oral care compositions, as described herein,physically separate the metal ion source from polyphosphates, silicaabrasives, or other chelants in a different nonwoven web layers, inseparate portions, in separate compositions of the oral carecompositions, or in a soluble solid phase. The physical separation ofthese components have been previously difficult to achieve. Unit-doseoral care compositions, such as pouches, solid foams, or soluble fibrouscompositions, provide the chassis that can physically separate metalions from other reactive components during storage, but also allows themto be combinable upon dissolution and/or disintegration in the oralcavity.

Morphology

The oral care composition, as described herein, can be described by itsmorphology, which is unique relative to other oral care compositions,such as dentifrice pastes and/or mouth rinses. For example, theunit-dose oral care composition comprising a fibrous composition can bea nonwoven web of fiber and/or filaments. The unit-dose oral carecomposition comprising a solid soluble foam composition can have voidswithin a solid foam network connected by struts. The solid soluble foamcompositions can have a mean void volume percentage, or the ratiobetween void-space to the total space occupied by the foam, of at leastabout 75%, at least about 85% or at least about 88%. In contrast, thefibrous compositions can have a mean void volume of from about 15% toabout 75%, from about 15% to about 70%, from about 30% to about 75%, orfrom about 35% to about 70%. Dentifrice pastes and/or mouth rinses wouldhave mean void volume percentages of less than 15% prior to use by aconsumer.

Solid soluble foam compositions can have an average pore size of greaterthan about 0.1 mm, greater than about 0.2 mm, or greater than about 0.3mm. In contrast, the fibrous compositions can have an average pore sizeof from about 0.001 mm to about 0.1 mm, from about 0.01 mm to about 0.05mm, or from about 0.01 mm to about 0.1 mm. Dentifrice pastes and/ormouth rinses would not be expected to have pores until use by a consumersince they are liquids and/or pastes.

Solid soluble foam compositions can have a surface area of from about 50mm⁻¹ to about 150 mm⁻¹, from about 75 mm⁻¹ to about 160 mm⁻¹, or fromabout 100 mm⁻¹ to about 150 mm⁻¹. In contrast, the surface of fibrouscompositions can be at least about 150 mm⁻¹, at least about 200 mm⁻¹, orat least about 250 mm⁻¹.

Examples

The following examples further describe and demonstrate embodimentswithin the scope of the present invention. The examples are given solelyfor the purpose of illustration and are not to be construed aslimitations of the present invention, as many variations thereof arepossible without departing from the spirit and scope of the invention.All exemplified amounts are concentrations by weight of the totalcomposition, i.e., wt/wt percentages, unless otherwise specified.

Unit-Dose Oral Care Compositions

Fibrous unit-dose oral care compositions were assembled from a fibrouscomposition and a nonfibrous composition. The fibrous composition, basedon TABLE 1, was made by first adding USP water to a batch mixing tank.The target amount of water is 60 wt % including the water introducedwith any aqueous components, thus, actual amount of the components addedvaries based on the batch size and the target composition. Next, thetarget amount of xylitol was added to the batch mixing tank while mixingat 60 rpm. The target amount of polyvinyl alcohol was added to the batchmixing tank. The batch mixing tank was heated to 80° C. The mixture washeated and stirred for 2 hours at 80° C. and 120 rpm.

The target amount of sodium lauryl sulfate and cocamidopropyl betainewere added in succession as aqueous solutions. Next, sucralose was thenadded to the mixture. Finally, the fluoride ion source was then added,if desired. The fibrous composition melt was allowed to degas over nightwhile being stirred at 70° C.

The fibrous composition melt was allowed to cool to 40° C. and thefibrous composition melt was spun into filaments and/or fibers. Thefibrous composition melt was transferred from the batch mixing tank tothe fiber spinning die. Fibers and/or filaments were extruded via aBiax-fiberfilm multi-row capillary die at 60° C. The fibers and/orfilaments were attenuated and dried with hot air to have less than 5%moisture. The fibers and/or filaments were collected on a belt as thefibrous composition.

The fibrous unit-dose compositions were assembled by placing a firststrip of the fibrous composition onto a die plate. Cavities in thefibrous composition were made by applying force within each die well.The nonfibrous composition was applied to the interior of the cavitywith a dropper. A second strip of fibrous composition was placed on topof the die plate. Pressure was applied to cut and bond the edges of thefirst and second fibrous composition layers. The dose was removed thedie cutter and the process was repeated for each dose.

TABLE 1 Unit-dose oral care compositions Ex. 1 Ex. 2 Ex. 3 Ex. 4 Ex. 5Location Ingredient (% wt) (% wt) (% wt) (% wt) (% wt) Fibrous Water1.60 1.60 1.49 1.55 2.22 Compostion SLS¹ 19.16 19.16 21.13 21.97 27.64Cocamido- 4.81 4.81 0.63 0.66 0.81 propyl Betaine Polyvinyl 16.42 16.4212.42 12.92 23.57 Alcohol² Sodium 2.74 2.74 2.49 2.59 4.29 SaccharinXylitol 0.96 5.61 11.68 12.15 20.36 Sodium 4.65 - - - - Gluconate SnF₂3.15 3.15 - - - NaF - - - - 2.31 Sucralose - - 0.15 0.16 0.27 NonfibtousFlavor 11.81 11.81 10.90 11.33 16.19 Composition Sodium 34.72 34.7232.05 33.33 - Hexameta- phosphate SnF₂ - - 2.91 3.03 - Sodium - -4.18 - - Gluconate CaCl₂ - - - - 1.90 ¹Powder ²Mixture of PVA403 andPVA420H

HAP Dissolution

The HAP dissolution method was designed to test the acid protection of achosen test dentifrice. After treating hydroxyapatite powder (HAP) withtest dentifrice slurries, the HAP is added to an acidic media and thechange in pH is an indicator of the degree of surface adsorption. Thesmaller the pH rise, the better the surface protection.

Dentifrice slurries (1:3 paste:water) were prepared for the comparativetreatment compositions listed in TABLE 2. Specifically, 10 g ofdentifrice paste was combined with 30 g of deionized water in a 50 mLcontainer with a stir bar. The container was placed on a stir plate tomix until the two components were mixed. The paste slurries werecentrifuged at 15,000 rpm for 15 min.

For each treatment, including for the water control, 0.300 g ofhydroxyapatite powder (HAP) was placed into a 50 mL round bottomcentrifuge tube. For treatment with a dentifrice paste, 24 mL of theprepared dentifrice slurry was added to the HAP. For treatment withExamples 1-4, 24 mL of water and 8 unit-doses of Examples 1-4 were addedto the HAP. Each treated HAP sample was immediately vortex mixed at 2500rpm for 2 minutes. All samples were then centrifuged at 15,000 rpm for15 minutes. The liquid phase was decanted out of the centrifuge tube,which left a HAP pellet. The remaining HAP pellet was rinsed three timesby adding deionized water, vortex mixing at 2500 rpm for 1 minute,centrifuging at 15,000 rpm for 15 minutes, and the liquid phase wasdecanted out of the centrifuge tube. The treated HAP pellet was dried ina 55° C. oven overnight.

Samples of HAP were then analyzed for fluoride ion uptake. 0.100 g ofthe dried and treated HAP was placed in a 50 mL Falco tube. 25 mL of0.5M perchloric acid was added to each Falco tube and each sample wasvortex mixed for 1 minute at 2500 rpm. A 1 mL aliquot of each digestedsample was added to a plastic vial. 1 mL of pH adjusted TISAB II (6:1TISAB II: 2N NaOH) was added to each sample. The fluoride content wasmeasured via a fluoride ion selective electrode (Beckman Coulter, Inc.,Pasadena, Calif., Cat. No. A51712).

Samples of HAP were analyzed for ApH. 25 mL of 10 mM citric acid (1.9212g of citric acid in 1 L of deionized water) was added to a 50 mL beakerwith a stir bar. The beaker was placed on a stir plate (Metrohm,Herisau, Switerland, Model No. 728) and turned on. The Titrano pHelectrode (Metrohm, Herisau, Switzerland, Model No. 719S) was placed inthe stirring beaker with citric acid. After equilibration of the citricacid solution (until pH has a minimum change of 2.5±0.001 pH within 30second), 50 mg of the dried HAP powder was added to the citric acidsolution. The pH was recorded at 5 min and 10 min. The % efficacy wasdetermined by Formula I, below.

$\begin{matrix}{{\% \mspace{14mu} {Efficacy}\mspace{14mu} {{vs}.\mspace{14mu} {CCP}}} = \frac{{{Average}\mspace{14mu} {\Delta pH}\mspace{14mu} {CCP}} - {{Average}\mspace{14mu} {\Delta pH}\mspace{14mu} {Treament}}}{{Average}\mspace{14mu} {\Delta pH}\mspace{14mu} {CCP}}} & {{Formula}\mspace{14mu} I}\end{matrix}$

Samples of HAP were analyzed for tin ion uptake by mixing 0.100 g of thedried and treated HAP with 25 mL of 90:10 (HNO₃:HBF₃) digestor. Analiquot of the digested HAP powder was analyzed for total tin ion uptakeby ICP-MS by comparison to the values of a curve of standardconcentrations of tin ions.

TABLE 2 Average F and Sn Uptake by HAP dissolution Average Average Sn F% Uptake Uptake Avg Efficacy vs. Treatment (ppm) (ppm) ΔpH CCP Water<500 136 1.36 −46.2 Crest ® Cavity <500 2286 0.93 0.00 Protection (CCP)Crest ® ProHealth ™ 4987 1038 0.77 17.2 Advanced (CPH) Example 1 341002182 0.49 47.3 Example 2 25800 2401 0.59 36.6 Example 3 33200 1832 0.6530.1 Example 4 32800 1773 0.63 32.3 Example 5 <500 5765 0.78 16.1

TABLE 2 shows the average Sn and F uptake by the HAP dissolutiondescribed herein. The average Sn uptake of the HAP sample treated withwater or CCP resulted in an average Sn uptake of <500 ppm. This was anexpected result as neither water nor CCP contained added tin ions, suchas SnF₂. Water showed an average F uptake of 136 ppm while CCP (0.243 wt% NaF) showed an average F uptake of 2286 ppm. CPH (0.454 wt % SnF₂ andsodium hexametaphosphate) showed an average Sn uptake of 4987 ppm and anaverage F uptake of 1038 ppm. The % efficacy of CPH vs. CCP was 17.2%,which indicated that there was 17.2% more surface protection of CPH onthe HAP powder than CCP. Thus, CPH was responsible for depositing Sn, F,and sodium hexametaphosphate on the HAP powder vs. F on the HAP powderfor CCP.

Example 1 had SnF₂ within the fibrous composition and sodiumhexametaphosphate in the nonfibrous composition. Despite beingformulated to theoretically calculated amount of fluoride ions (and byextension stannous ions), Example 1 had an average Sn uptake of 34100ppm (nearly 7× more) and an average F uptake of 2182 ppm (2× more).Additionally, the % efficacy vs. CCP for Example 1 was 47.3% (3× higherthan CPH).

As shown in TABLE 2, Example 2 was identical to Example 1 (SnF₂ infibrous composition and sodium hexametaphosphate in the nonfibrouscomposition), but Example 2 did not contain a chelant, sodium gluconate.Example 1 had sodium gluconate in the fibrous composition, which wasused to weakly associate with tin ions to prevent irreversible bindingwith other dentifrice components, such as sodium hexametaphosphate inaqueous solutions. Example 2 had an average Sn uptake of 25800 ppm (5×higher than CPH) and an average F uptake of 2401 ppm (2× more than CPH).Additionally, the % efficacy vs. CCP for Example 1 was 36.6% (2× higherthan CPH). While Example 2 led to more surface absorption than CPH,Example 2 performed slightly worse than Example 1. Thus, while a chelantcan be used to improve Sn uptake and total absorption, a chelant, suchas gluconate, was not needed to outperform CPH.

As in TABLE 2, Example 3 was similar to the composition of Example 1,but the SnF₂ and sodium gluconate were placed in the nonfibrouscomposition with sodium hexametaphosphate. These compounds were in thesolid phase (i.e. not dissolved or dispersed in a solvent) until hittingthe aqueous treatment solution, effectively simulating the use of theunit-dose dentifrice in the oral cavity.

Example 3, outperformed Example 2 and CPH, but did not reach the %efficacy or Sn uptake as Example 1, where the polyphosphate and SnF₂were stored in separate phases. Example 4 was similar to Example 3,except without the sodium gluconate chelant. As expected, the removal ofthe chelant led to a slightly worse performance compared with Example 3,but still a superior performance relative to commercially availabledentifrice compositions, such as CPH or CCP.

Example 5 had NaF in the fibrous composition and CaCl₂) in thenon-fibrous composition. The average F uptake was 5765 ppm, which wassignificantly higher than the corresponding paste dentifrice, CCP, whichhad an average F uptake of 2286 ppm, despite being formulated to providethe same number of total F ions. Thus, Example 5 had significantlyhigher amounts of bioavailable F ions, or F ions which were not tied updue to reactivity with other components.

Some of the increase in fluoride uptake likely occurred from adsorptionof F on the HAP surface while some likely occurred because of formationof CaF₂, during analysis, which was recovered during centrifugation.This is consistent with the observation that some of the particles didnot wet completely suggesting a new particle was formed. In the oralcavity, instantaneous formation of CaF₂ upon dissolution may increasethe retention and availability of fluoride over the course of minutes tohours as the deposited CaF₂ can slowly interact with the HAP.

While it was normally expected that Ca and F would react prior todeposition in the oral cavity, physically separating Ca (in thenonfibrous composition) and F (in the fibrous composition) unexpectedlyresulted in a superior average F uptake and the observation of CaF₂deposition (vs. adsorption) on the surface of HAP. While not wishing tobe being bound by theory, the same result is expected to occur if Ca informulated in the fibrous composition and the fluoride ions source is inthe nonfibrous composition, if both ions are present as solid particles(i.e. not at least partially dissolved in a solvent) in the samecomposition, such as in the nonfibrous composition, or dissolved in alow water (<25% water) solvent added to the nonfibrous composition.

Enamel Fluoride Uptake

The Enamel Fluoride Uptake by FDA Method 40 is a method used todetermine the amount of fluoride delivered to demineralized enamelspecimens from a single 30-minute treatment of 1:3 dentifrice slurry.

A core of sound human enamel with a diameter of 3-4 mm was extractedfrom whole human teeth. The cores were mounted on an acrylic rod and thesurfaces were ground using 600 grit. The cores were then polished with0.05p polish (Alumina Suspension Gamma B, MetLab Corp, catalog#M303-128). Specimens were stored in an airtight container above a smallamount of deionized water (˜1-5 mL) in a standard laboratoryrefrigerator (˜2-4° C.).

Each enamel specimen was inspected and samples with large cracks oruneven calcification were discarded. Specimens were polished again for10 minutes using 0.05p polish. Samples were sonicated with a sonicatorin deionized water for 15-30 min. Enamel specimens were then rinsed withstandard deionized water and wiped to remove any residual polish.

Enamel specimens were then demineralized. 25 mL of MHDP(N-2-hydroxyethyl, methane hydroxy diphosphonate) demineralizationsolution (0.025M lactic acid, 2×10⁻⁴M MHDP) was placed in a 30 mLplastic vial for each specimen. An enamel specimen was placed on the capof each vial. Each cap was placed on the top of the vial to submerge theenamel specimen in the MHDP demineralization solution. The enamelspecimen was not allowed to touch the bottom of the vial. Specimens wereleft in the demineralization solution for 48 hours at ambient conditionsto form artificial caries lesions. The rods were tapped twice daily toremove any bubbles. After 48 hours, specimens were removed from thedemineralization solution and rinsed thoroughly with deionized water.

If the sample was a paste dentifrice, 10 g of dentifrice was placed in a50 mL tri-pour plastic beaker. 30 mL of deionized water was added to thebeaker. An x-shaped stir bar was placed on top of the dentifrice in eachbeaker and the beaker was placed on a magnetic stir plate. Thedentifrice was broken up with a wooden stick until the stir bar iscapable of spinning freely at 300-400 rpm. The dentifrice slurry wasstirred for 20 minutes. The slurry was transferred to a centrifuge tubeand centrifuged for 30 minutes at 11,000 rpm.

If the sample was a solid dentifrice, 10 doses of the solid formdentifrice was weighed and placed in a 50 mL tri-pour plastic beaker.Deionized water was added to bring the combined water and sample mass to10 g. 30 mL of additional deionized water was then placed in the beaker.An x-shaped stir bar was placed on top of the dentifrice in each beakerand the beaker was placed on a magnetic stir plate. The slurry was mixedat 300-400 rpm for 20 minutes. The slurry was transferred to acentrifuge tube and centrifuged for 30 minutes at 11,000 rpm.

Slurry supernatants (for the solid and paste forms) were decanted into a50 mL tri-pour plastic beaker. An x-shaped stir bar was placed in thebeaker and the beaker was placed on a magnetic stir plate. The stirplate was turned to 300-400 rpm. Lesioned enamel specimens weresuspended into each treatment. Each sample was treated for 30 minutes.After 30 minutes, each sample was rinsed with deionized water. Sampleswere stored in an airtight container above a small amount of deionizedwater (˜1-5 mL) in a standard laboratory refrigerator (˜2-4° C.).

The samples were analyzed for fluoride content analysis by collectingthe milled enamel powder following drilling and dissolving that enamelin acid then neutralizing and buffering it. Upon drilling a sample fromthe enamel specimen, the area of the enamel drilled was recorded.

Fluoride uptake was directly measured using a Fluoride Ion SpecificElectrode (Thermo Scientific, Orion, 96-09-00, Waltham, Mass.). Eachspecimen sample was placed on the end of the electrode. A value of mVwas recorded. This value was converted to ppm fluoride by using astandard curve of prepared fluoride standards. Fluoride uptake wascalculated by dividing the mass of fluoride in μg by the total areasampled with the microdrill biopsy.

The Enamel Fluoride Uptake method is based upon FDA Test Method #40. Theresults for enamel fluoride uptake are provided in TABLE 4.

Mean Fluoride Released

A stock fluoride solution (0.5 mg/mL, 500 ppm, Ricca, RC3172-16,Arlington, Tex.) was diluted to make solutions of 25 ppm, 50 ppm, and250 ppm using deionized water. Each standard was diluted at a 1:1 ratiowith TISAB II (Ricca, RC867016, Arlington, Tex.) buffer solution tocreate calibration solutions.

A calibration curve was created using the calibration solutions. 200 μLof 25 ppm calibration solution was placed in a microsample cup. Afluoride electrode was placed in the solution and the mV of each sampleis noted. The procedure was repeated for each prepared calibrationsolution. A calibration curve was constructed by plotting mV vs. Log[F—].

Paste dentifrice samples were prepared by weighing approximately 4 g ofeach paste sample in a 70 mL speed mixer cup. Solid dentifrice sampleswere prepared by weighing 4 doses of each dentifrice samples and addingdeionized water to QS at 4 g. Next, 12 mL of deionized was added to thesample cup. The speed mixer cup was mixed for 60 seconds (FlackTekSpeedmixer, Landrum, S.C.) using Speedmixer Program #7, which is 800 rpmfor 5 seconds and then 2200 rpm for 55 seconds. The slurry samples weretransferred into a centrifuge tube and then centrifuged for 10 minutesat 11,000 rpm.

Samples were prepared for analysis by combining 1 mL of the supernatantand 1 mL of fresh TISAB II buffer. The samples were quickly mixed usinga vortex mixer. 200 μL of the solution were transferred to a microsample cup. The fluoride electrode was placed in the cap. The value (mV)was recorded.

Values for released fluoride were calculated using Formula 1, providedbelow.

$\begin{matrix}{{{Percent}\mspace{14mu} {Fluoride}\mspace{14mu} {Released}} = \frac{{{Average}\mspace{14mu}\lbrack F\rbrack}\mspace{14mu} {ppm}\mspace{14mu} X\mspace{14mu} {Dilution}\mspace{14mu} {Factor}\mspace{14mu} X\mspace{14mu} 100}{{Labeled}\mspace{14mu} {Fluoride}\mspace{14mu} {Level}}} & {{Formula}\mspace{14mu} 1}\end{matrix}$

[F]=Fluoride Concentration of Sample Supernatant (ppm)

Dilution Factor:

NaF and SnF₂=4−(Formula % Insoluble Raw Materials/100)

*Tnsoluble Raw Materials (IRM) include silica, titanium dioxide, mica,and prills.

TABLE 3 Compositions Tested Ex. 6 Ex. 7 Ex. 8 Ex. 9 Components (wt %)(wt %) (wt %) (wt %) Distilled Water 3.0 3.0 13.0 3.0 Polyvinyl 24.2629.10 — — Alcohol¹ Sodium 4.85 4.85 — — Saccharin Sodium Lauryl 16.9819.40 — — Sulfate (powder) Sodium Lauryl 25.46 14.55 — — Sulfate(solution) Sorbitol 20.61 1.67 — 20.23 Cocamidopropyl 2.43 8.49 — —betaine Sodium — 13.05 — — Gluconate Citric Acid — 0.02 — — PVP K60 — —82.46 — PVOH — — — 72.27 NaF 2.43 — — — SnF₂ — 5.87 4.54 4.50 Total 100100 100 100 ¹Mixture of PVA403 and PVA420H

TABLE 4 Average Fluoride Uptake Formulation Fluoride Average FluorideTreatment Level (ppm) Uptake (μg F/cm²) NaF USP^(a) 1100 8.45 SnF₂USP^(b) 1100 10.00 Ex. 6 1100 9.32 Ex. 7 1100 23.33^(c) Ex. 8 1100 8.76Ex. 9 1100 5.27 ^(a)USP sodium fluoride standard in water ^(b)USPstannous fluoride standard in water ^(c)Average of two treatmentregimens

TABLE 4 shows the average fluoride uptake of Ex. 6-9 compared with a NaFUSP standard and a SnF USP standard according to FDA method #40 asdescribed herein. Ex. 6-9 are formulated to theoretically provide 1100ppm of fluoride. Ex. 6 (NaF) had an average fluoride uptake of 9.32 μgF/cm² while the Na USP standard had an average fluoride uptake of 8.45μg F/cm². Thus, a unit dose oral care composition that isolates fluoridefrom other reactive components of a toothpaste, as described herein andshown by Ex. 6, outperformed a NaF USP standard.

Additionally, Ex. 7 (SnF₂) had an average fluoride uptake of 23.33 μgF/cm² while the SnF₂ USP standard had an average uptake of 10.00 μgF/cm². The average fluoride uptake of Ex. 7 was so unexpectantly highthat a second run was performed to confirm the result. Thus, a unit doseoral care composition that isolates fluoride from other reactivecomponents of a toothpaste, as described herein and shown by Ex. 7,outperformed a SnF₂ USP standard.

TABLE 5 1 Minute Fluoride Release Formulation Mean Fluoride MeanFluoride Fluoride Level Released Released Treatment (ppm) (ppm) (%) Ex.6 1100 1062.0 96.5 Ex. 7 1100 1088.9 99.0 Ex. 8 1100 808.2 73.5 Ex. 91100 1017.1 92.5 Crest ® Cavity 1100 1004.0 91.3 Protection (NaF) SnF₂USP (SnF₂) 1100 796.4 72.4

TABLE 5 shows the 1 minute fluoride release of the unit dose oral carecompositions of TABLE 3. Ex. 6 (NaF) and Ex. 7 (SnF₂) released 96.5% and99.0% of its fluoride ions within 1 minute of contacting water. Incomparison, dentifrice compositions, such as Crest® Cavity Protectionand SnF₂ USP only released 91.3% and 72.4%, respectively, of fluorideions by 1 minute. Thus, the unit-dose oral care compositions of Ex. 6and 7 can outperform conventional dentifrice compositions by releasingbiologically available fluoride ions within 1 minute. Without wishing tobeing bound by theory, a quick release of fluoride ions can beadvantageous because individuals using dentifrice compositions toprovide fluoride may not always brush with the dentifrice compositionsfor a long enough time to receive the full benefit of the dentifricecompositions.

Every document cited herein, including any cross referenced or relatedpatent or application and any patent application or patent to which thisapplication claims priority or benefit thereof, is hereby incorporatedherein by reference in its entirety unless expressly excluded orotherwise limited. The citation of any document is not an admission thatit is prior art with respect to any invention disclosed or claimedherein or that it alone, or in any combination with any other referenceor references, teaches, suggests or discloses any such invention.Further, to the extent that any meaning or definition of a term in thisdocument conflicts with any meaning or definition of the same term in adocument incorporated by reference, the meaning or definition assignedto that term in this document shall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are within the scope of this invention.

What is claimed is:
 1. A solid unit-dose oral care compositioncomprising: (a) sodium monofluorophosphate; (b) abrasive, the abrasivecomprising calcium carbonate, dicalcium phosphate, tricalcium phosphate,calcium orthophosphate, calcium metaphosphate, calcium polyphosphate,calcium hydroxyapatite, or combinations thereof; and (c) sugar alcohol,the sugar alcohol comprising xylitol, sorbitol, mannitol, maltitol,lactitol, isomalt, erythritol, or combinations thereof.
 2. The solidunit-dose oral care composition of claim 1, wherein the sugar alcoholcomprises xylitol and mannitol.
 3. The solid unit-dose oral carecomposition of claim 1, wherein the abrasive comprises calcium carbonateand dicalcium phosphate.
 4. The solid unit-dose oral care composition ofclaim 1, wherein the abrasive comprises silica, sodium bicarbonate, orcombinations thereof.
 5. The solid unit-dose oral care composition ofclaim 1, wherein the oral care composition further comprises sodiumcocoyl glutamate.
 6. The solid unit-dose oral care composition of claim1, wherein the oral care composition is a tablet.
 7. The solid unit-doseoral care composition of claim 1, wherein the abrasive comprises calciumcarbonate, dicalcium phosphate, sodium bicarbonate, and silica.
 8. Thesolid unit-dose oral care composition of claim 7, wherein the sugaralcohol comprises xylitol and mannitol.
 9. The unit-dose oral carecomposition of claim 8, wherein the solid unit-dose oral carecomposition comprises polyvinylpyrrolidone.
 10. The unit-dose oral carecomposition of claim 9, wherein the solid unit-dose oral carecomposition comprises cellulose derivative.
 11. A solid unit-dose oralcare composition comprising: (a) fluoride; (b) abrasive, the abrasivecomprising calcium carbonate and dicalcium phosphate; and (c) sodiumcocoyl glutamate.
 12. The solid unit-dose oral care composition of claim11, wherein the oral care composition comprises sugar alcohol.
 13. Thesolid unit-dose oral care composition of claim 12, wherein the sugaralcohol comprises xylitol, mannitol, or combinations thereof.
 14. Thesolid unit-dose oral care composition of claim 11, wherein the fluoridecomprises sodium monofluorophosphate, sodium fluoride, stannousfluoride, amine fluoride, or combinations thereof.
 15. The solidunit-dose oral care composition of claim 11, wherein the abrasivecomprises silica, sodium bicarbonate, or combinations thereof.
 16. Thesolid unit-dose oral care composition of claim 11, wherein the oral carecomposition is a tablet.
 17. The unit-dose oral care composition ofclaim 11, wherein the solid unit-dose oral care composition comprisespolyvinylpyrrolidone.
 18. The unit-dose oral care composition of claim11, wherein the solid unit-dose oral care composition comprisescellulose derivative.
 19. A unit-dose dentifrice tablet compositioncomprising: (a) sodium monofluorophosphate; (b) abrasive, the abrasivecomprising calcium carbonate and dicalcium phosphate; (c) sugar alcohol,the sugar alcohol comprising xylitol and mannitol; and (d) sodium cocoylglutamate.
 20. The unit-dose dentifrice tablet composition of claim 19,wherein the composition comprises polyvinylpyrrolidone.